Potential Host Manipulation by the Aphid Parasitoid Aphidius avenae to Enhance Cold Tolerance.

During parasitoid development, the immature parasitoid is confined to the host species. As a result, any potential to modify the physiology or behaviour of the host could play an important role in parasitoid fitness. The potential for host manipulation by the aphid parasitoid Aphidius avenae to increase cold thermotolerance was investigated using the aphid host species Metopolophium dirhodum and Sitobion avenae. Aphids were parasitized at L3/L4 instar stage (5 d old) and allowed to develop into pre-reproductive adults (10 d old) containing a 5 d old parasitoid larva. A control group was created of non-parasitized pre-reproductive adults (10 d old). The inherent physiological thermotolerance (LT50) and potential behavioural thermoregulation (behaviour in a declining temperature regime) of parasitized and non-parasitized aphids were investigated. Results revealed no effect of parasitism on the physiological thermotolerance of S. avenae and M. dirhodum. Significant differences in the behaviour of parasitized and non-parasitized aphids were observed, in addition to differences between host species, and such behaviours are discussed in view of the potential for host manipulation.

Masculinised Behaviour of XY Females in a Mammal with Naturally Occuring Sex Reversal.

Most sex differences in phenotype are controlled by gonadal hormones, but recent work on laboratory strain mice that present discordant chromosomal and gonadal sex showed that sex chromosome complement can have a direct influence on the establishment of sex-specific behaviours, independently from gonads. In this study, we analyse the behaviour of a rodent with naturally occurring sex reversal: the African pygmy mouse Mus minutoides, in which all males are XY, while females are of three types: XX, XX* or X*Y (the asterisk represents an unknown X-linked mutation preventing masculinisation of X*Y embryos). X*Y females show typical female anatomy and, interestingly, have greater breeding performances. We investigate the link between sex chromosome complement, behaviour and reproductive success in females by analysing several behavioural features that could potentially influence their fitness: female attractiveness, aggressiveness and anxiety. Despite sex chromosome complement was not found to impact male mate preferences, it does influence some aspects of both aggressiveness and anxiety: X(*)Y females are more aggressive than the XX and XX*, and show lower anxiogenic response to novelty, like males. We discuss how these behavioural differences might impact the breeding performances of females, and how the sex chromosome complement could shape the differences observed.

Synthesis of E-Alkyl Alkenes from Terminal Alkynes via Ni-Catalyzed Cross-Coupling of Alkyl Halides with B-Alkenyl-9-borabicyclo[3.3.1]nonanes.

The first Ni-catalyzed Suzuki-Miyaura coupling of alkyl halides with alkenyl-(9-BBN) reagents is reported. Both primary and secondary alkyl halides including alkyl chlorides can be coupled. The coupling method can be combined with hydroboration of terminal alkynes, allowing the expedited synthesis of functionalized alkyl alkenes from readily available alkynes with complete (E)-selectivity in one pot. The method was applied to the total synthesis of (±)-Recifeiolide, a natural macrolide.

A Functional Group Approach for Prediction of APPI Response of Organic Synthetic Targets.

Atmospheric pressure photoionization (APPI) is a technique of choice for ionization of non-polar molecules in mass spectrometry (MS). Reported APPI-based studies tend to focus on a selected compound class, which may contain a variety of functional groups. These studies demonstrate that APPI response frequently differs substantially, indicating a certain dependence on the functional group present. Although this dependence could be employed for APPI response prediction, its systematic use is currently absent. Here, we apply APPI MS to a judiciously-compiled set of 63 compounds containing a number of diverse functional groups commonly utilized in synthesis, reactive functional groups, as well as those containing boron and silicon. Based on the outcome of APPI MS of these compounds, we propose and evaluate a simple guideline to estimate the APPI response for a novel compound, the key properties of which have not been characterized in the gas phase. Briefly, we first identify key functional groups in the compound and gather knowledge on the known ionization energies from the smallest analogues containing said functional groups. We then consider local inductive and resonance effects on said ionization energies for the compounds of interest to estimate the APPI response. Finally, application of APPI MS to compounds of interest considered herein demonstrated extended upper mass ionization limit of 3.5 kDa for non-polymeric compounds.

Nickel-catalyzed diastereoselective alkyl-alkyl Kumada coupling reactions.

A nickel pincer complex is found to catalyze alkyl-alkyl Kumada coupling reactions of 1,3- and 1,4-substituted cyclohexyl halides and tetrahydropyrans with an excellent diastereoselectivity. The mechanistic investigation of the coupling reactions provides evidence that the activation of alkyl halides is reversible.