Cultured skin microbiota attracts malaria mosquitoes

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Chemical Mediation of Oviposition by Anopheles Mosquitoes : a Push-Pull System Driven by Volatiles Associated with Larval Stages

The oviposition behavior of mosquitoes is mediated by chemical cues. In the malaria mosquito Anopheles gambiae, conspecific larvae produce infochemicals that affect this behavior. Emanations from first instar larvae proved strongly attractive to gravid females, while those from fourth instars caused oviposition deterrence, suggesting that larval developmental stage affected the oviposition choice of the female mosquito. We examined the nature of these chemicals by headspace collection of emanations of water in which larvae of different stages were developing. Four chemicals with putative effects on oviposition behavior were identified: dimethyldisulfide (DMDS) and dimethyltrisulfide (DMTS) were identified in emanations from water containing fourth instars; nonane and 2,4-pentanedione (2,4-PD) were identified in emanations from water containing both first and fourth instars. Dual-choice oviposition studies with these compounds were done in the laboratory and in semi-field experiments in Tanzania. In the laboratory, DMDS and DMTS were associated with oviposition-deterrent effects, while results with nonane and 2,4-PD were inconclusive. In further studies DMDS and DMTS evoked egg retention, while with nonane and 2,4-PD 88% and 100% of female mosquitoes, respectively, laid eggs. In dual-choice semi-field trials DMDS and DMTS caused oviposition deterrence, while nonane and 2,4-PD evoked attraction, inducing females to lay more eggs in bowls containing these compounds compared to the controls. We conclude that oviposition of An. gambiae is mediated by these four infochemicals associated with conspecific larvae, eliciting either attraction or deterrence. High levels of egg retention occurred when females were exposed to chemicals associated with fourth instar larvae.</p

Composition of Human Skin Microbiota Affects Attractiveness to Malaria Mosquitoes

The African malaria mosquito Anopheles gambiae sensu stricto continues to play an important role in malaria transmission, which is aggravated by its high degree of anthropophily, making it among the foremost vectors of this disease. In the current study we set out to unravel the strong association between this mosquito species and human beings, as it is determined by odorant cues derived from the human skin. Microbial communities on the skin play key roles in the production of human body odour. We demonstrate that the composition of the skin microbiota affects the degree of attractiveness of human beings to this mosquito species. Bacterial plate counts and 16S rRNA sequencing revealed that individuals that are highly attractive to An. gambiae s.s. have a significantly higher abundance, but lower diversity of bacteria on their skin than individuals that are poorly attractive. Bacterial genera that are correlated with the relative degree of attractiveness to mosquitoes were identified. The discovery of the connection between skin microbial populations and attractiveness to mosquitoes may lead to the development of new mosquito attractants and personalized methods for protection against vectors of malaria and other infectious diseases

In the Pursuit for Better Actinide Ligands: An Efficient Strategy for their Discovery\ud

A novel method for the efficient discovery of new types of minor actinide (MA) ligands is based on the unique combination of “tea bag” split pool combinatorial chemistry and screening based on the inherent radioactivity of the complexed cations. Four multicoordinating Am3+ chelating groups, such as CMPO (diphenylcarbamoylmethyl)phosphine oxide), PICO (picolinamide), DGA (N,N′-dimethyldiglycoldiamide), and MPMA (N-methyl-N-phenylmalonamide), on a trityl platform immobilized on TentaGelS served as a model library for the development of the screening method. This model library was screened under various conditions (i.e., 0.001 M ≤ [HNO3] ≤ 3 M, NaNO3 ≤ 4 M, and [Eu] ≤ 10 × [ligand]) showing competitive extraction of the four ligands. Other libraries of 9 and 72 members were synthesized by functionalization of the trityl platform with ligating groups that are composed of four building blocks (including at least one amide and one (phosphoric) hydrazone moiety). The screening of these two libraries resulted in the discovery of two multicoordinate ligands that contain ligating groups previously not known to complex Am3+. Both are N-isopropyl amides terminated with a p-methoxyphenyl hydrazide (A2B1C1D10 KD(Am) = 2197) or a p-nitrophenyl hydrazide (A2B1C1D11 KD(Am) =1989) moiety, respectively. They are more efficient than the immobilized tritylCMPO ligand (KD(Am) = 1280) at 3 M HNO3. This method has the advantages of a high analytical sensitivity and the direct comparison of the extraction results. The method also allows the competitive screening of multiple nuclides which can be quantified by their radioactive emission spectru

Thiacalix(4)arene derivatives as radium ionophores: a study on the requirements for Ra2+ extraction

The synthesis and NOE-based structural characterization is described of thiacalix[4]arene tricarboxylic acid ( 7), thiacalix[4]crown-5 and -6 monocarboxylic acids ( 2 and 5), and the bis(N-methylsulfonyl)thiacalix[4]crowns-5 and -6 ( 4a,b). The 226Ra2+ selectivity coefficients, log(KRaex/KMex), of the new thiacalix[4]arene derivatives are compared directly with those of thiacalix[4]crown-5 and -6 ( 1a,b), thiacalix[4]crown-5 and -6 dicarboxylic acids ( 3a,b), and thiacalix[4]arene di- and tetracarboxylic acids ( 6 and 8). Thiacalix[4]arene dicarboxylic acid ( 6) already exhibits a high 226Ra2+ selectivity, but this is significantly improved in the case of 3b, having an additional crown-(6-)ether bridge. The covalent combination of a crown ether and carboxylic acid substituents as in the thiacalix[4]arenes 2, 3a,b, 4a,b, and 5 gives a better 226Ra2+ selectivity in the presence of Sr2+ or Ba2+ than mixtures of dibenzo-21-crown-7 and thiacalix[4]arene dicarboxylic acid ( 6) or of pentadecanoic acid and thiacalix[4]crown-6 ( 1b)

Cation control on the synthesis of p-t-butylthiacalix[4]-(bis)crown ethers

Bridging of p-t-butylthiacalix[4]arene with ethylene glycol ditosylates gave diametrically bridged thiacalix[4]monocrowns-4 and -5, 1,2-alternate thiacalix[4]biscrowns-4 and -5 and 1,3-alternate thiacalix[4]biscrown-5, dependent on the metal carbonate used. They show excellent extraction ability towards Ag+ cations.\ud The synthesis of novel diametrically and proximally substituted p-t-butylthiacalix[4](bis)crown ethers and their extraction behavior towards monovalent metal ions are presented

Synthesis and Conformational Evaluation of p-tert-Butylthiacalix[4]arene-crowns

Bridging of p-tert-butylthiacalix[4]arene afforded 1,3-dihydroxythiacalix[4]arene-monocrown-5 (3b), 1,2-alternate thiacalix[4]arene-biscrown-4 and -5 (4a,b), and 1,3-alternate thiacalix[4]arene-biscrown-5 and -6 (5a,b), depending on the metal carbonates and oligoethylene glycol ditosylates used. Starting from 1,3-dialkylated thiacalix[4]arenes, the corresponding bridging reaction gave 1,3-alternate, partial-cone, and cone conformers 10-19, depending on the substituents present. Temperature-dependent studies revealed that the conformationally flexible 1,3-dimethoxythiacalix[4]arene-crowns 10a-c exclusively occupy the 1,3-alternate conformation. Demethylation exclusively gave the cone 1,3-dihydroxythiacalix[4]arene-crowns (3a,c), which could not be obtained by direct bridging of thiacalix[4]arene. The different structures were assigned on the basis of several X-ray crystal structures and extensive 2-D 1H NMR studies

Selective removal of 226Ra2+ from gas-field-produced waters

The 226Ra2+ selectivity of both the self-assembled (iso)guanosine-based systems and ionizable thiacalix[4]crown dicarboxylic acids was determined in gas-field-produced water and a metal ion-containing model solution (simulant). Seven gas-field-produced water samples have been analyzed. From a sample (K5D) with average metal ion concentrations ([metaltot] = 0.14 M), thiacalix[4]crown-5 dicarboxylic acid (10-4 M) extracts 60% of the 226Ra2+ content. Extractions performed with the model solution (MK5D) indicate that in K5D there is significant competition in 226Ra2+ extraction due to the organic constituents of K5D, in particular with self-assembled extractants guanosine and isoguanosine. Nevertheless, all four extractants extract 226Ra2+ both from the produced water K5D and the model solution MK5D, even with a 100-fold excess of [metaltot] to [extractant]. The extracted 226Ra2+ cations could effectively be stripped from the extractants by washing with pH 2 water. The results obtained with the extractants used, especially thiacalix[4]crown-5 dicarboxylic acid 3, clearly demonstrate the way to selectively remove Ra2+ from gas-field-produced waters

Multiple ionic interactions for noncovalent synthesis of molecular capsules in polar solar

The formation and characterization of molecular capsules resulting from the self-assembly between oppositely charged (thia)calix[4]arenes in polar solvents like MeOH and MeOH–H2O are reported. The multiple ionic interactions allow the self-assembly of the complementary (thia)calix[4]arenes 1 and 2a–d into 11 complexes as revealed by 1H NMR and mass spectrometry (ESI-MS). Isothermal titration calorimetry (ITC) was used to determine the association constants, which, depending on the ionic groups involved in the complexes, vary between 103 and 106 M–1. An X-ray structure of the assembly 1 2d was also obtained. Unlike in solution, in the solid state 1 2d forms a 11 three-dimensional network in which 2d adopts a 1,2-alternate conformation