Chiral amplification can be switched ON/OFF to both helical senses by the presence/absence of metal ions in copolymers of poly(phenylacetylene)s.

Os conteúdos das glândulas metatorácicas de insetos adultos do percevejo Dichelops melacanthus (Hemiptera: Pentatomidae) foram analisados. Os compostos de defesa foram identificados combinando as técnicas de cromatografia gasosa (CG), cromatografia gasosa acoplada à espectrometria de massas (CG-EM) e por comparação de seus índices de retenção com os de compostos padrões. Tridecano foi o componente majoritário, seguido de quantidades menores e aproximadamente iguais de (E)-4-oxo-2-hexenal e (E)-2-octenal. Também foram identificados (E)-2-hexenal, decano, acetato de (E)-2-hexenila, undecano, (E)-4-oxo-2-octenal, dodecano, acetato de (E)-2-octenila, 1-trideceno, tetradecano e pentadecano.The contents of metathoracic glands of adults of the stink bug Dichelops melacanthus (Hemiptera: Pentatomidae) were analyzed. Compounds were identified by gas chromatography (GC), coupled GC-mass spectrometry and matching retention indices and mass spectra with those of authentic samples. Tridecane was the major component followed by lesser and approximately equal amounts of (E)-4-oxo-2-hexenal and (E)-2-octenal. Other compounds identified include (E)-2-hexenal, decane, (E)-2-hexenyl acetate, undecane, (E)-4-oxo-2-octenal, dodecane, (E)-2-octenyl acetate, 1-tridecene, tetradecane and pentadecane.Keywords: Dichelops melacanthus, defensive compounds, short-chain unsaturated aldehydes, unsaturated acetates, tridecane IntroductionInsects have evolved a multitude of chemical and behavioral defenses against other offensive organisms. Stink bugs, as their name suggests, produce large quantities of strong-smelling and irritating defensive chemicals, which are released when the bugs are disturbed or molested. 1In general, heteropterans produce allomones in dorsal abdominal scent glands as immatures, and in metathoracic scent glands as adults. [1][2][3] Numerous reports attest to the efficacy of the secretions of the metathoracic and abdominal scent glands as effective defenses against predation. 1,2,4 They also may have a role as alarm pheromones, 5 as has been demonstrated for similar types of compounds produced by bug species in other families. 6,7 Stink bug defensive compounds have received considerable study, and it has been shown that the types of compounds constituting the defensive chemical blends typically consist of alkane hydrocarbons and saturated and unsaturated aldehydes and esters. In adults, the defensive compounds are produced in large, well-defined, and usually colored metathoracic glands, which are not present in the immature stages.Sex pheromones have been identified from only a few phytophagous stink bug species to date. 8,9 In all cases reported, components from metathoracic glands have not been part of the pheromone blend. However, because stink bugs readily release defensive compounds when disturbed, it is difficult if not impossible to collect extracts of sex pheromones uncontaminated by these components.The main objective of this study was to characterize the defensive compounds produced in the metathoracic glands o...

The preparation and synthetic applications of selenium‐ and tellurium‐stabilized carbanions as well as selenonium and telluronium ylides are reviewed. Selenium‐ and tellurium‐stabilized carbanions are prepared by deprotonation or by element/lithium exchange of the parent selenides and tellurides. Additionally, selenium‐stabilized carbanions are prepared by conjugate addition of organometallics to vinyl‐ and alkynyl selenides. Selenonium and telluronium ylides are prepared mainly by deprotonation of the parent selenonium and telluronium salts. The above‐mentioned anionic species react with electrophiles, giving intermediates, which by subsequent transformations, lead to synthetically useful products. In the case of the selenium‐stabilized carbanions, these sequences of reactions were applied in the synthesis of natural products. The tellurium counterparts were not yet explored for this purpose. Selenonium and telluronium ylides were not yet employed in total synthesis.

Metals capped with organochalcogenides have attracted considerable interest due to their practical applications, which include catalysis, sensing, and biosensing, due to their optical, magnetic, electrochemical, adhesive, lubrication, and antibacterial properties. There are numerous reports of metals capped with organothiol molecules; however, there are few studies on metals capped with organoselenium or organotellurium. Thus, there is a gap to be filled regarding the properties of organochalcogenide systems which can be improved by replacing sulfur with selenium or tellurium. In the last decade, there has been significant development in the synthesis of selenium and tellurium compounds; however, it is difficult to find commercial applications of these compounds because there are few studies showing the feasibility of their synthesis and their advantages compared to organothiol compounds. Stability against oxidation by molecular oxygen under ambient conditions is one of the properties which can be improved by choosing the correct organochalcogenide; this can confer important advantages for many more suitable applications. This paper reports the successful synthesis and characterization of gold nanoparticles functionalized with organochalcogenide molecules (dibutyldisulfide, dibutyl-diselenide and dibutyl-ditelluride) and evaluates the oxidation stability of the organochalcogenides. Spherical gold nanoparticles with diameters of 24 nm were capped with organochalcogenides and were investigated using X-ray photoelectron spectroscopy (XPS) to show the improved stability of organoselenium compared with organothiol and organotellurium. The results suggest that the organoselenium is a promising candidate to replace organothiol because of its enhanced stability towards oxidation by molecular oxygen under ambient conditions and its slow oxidation rate. The observed difference in the oxidation processes, as discussed, is also in agreement with theoretical calculations.

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BackgroundResistance to fluconazole, a commonly used azole antifungal, is a challenge for the treatment of fungal infections. Resistance can be mediated by overexpression of ABC transporters, which promote drug efflux that requires ATP hydrolysis. The Pdr5p ABC transporter of Saccharomyces cerevisiae is a well-known model used to study this mechanism of antifungal resistance. The present study investigated the effects of 13 synthetic compounds on Pdr5p.ResultsAmong the tested compounds, four contained a tellurium-butane group and shared structural similarities that were absent in the other tested compounds: a lateral hydrocarbon chain and an amide group. These four compounds were capable of inhibiting Pdr5p ATPase activity by more than 90%, they demonstrated IC50 values less than 2 μM and had an uncompetitive pattern of Pdr5p ATPase activity inhibition. These organotellurides did not demonstrate cytotoxicity against human erythrocytes or S. cerevisiae mutant strains (a strain that overexpress Pdr5p and a null mutant strain) even in concentrations above 100 μM. When tested at 100 μM, they could reverse the fluconazole resistance expressed by both the S. cerevisiae mutant strain that overexpress Pdr5p and a clinical isolate of Candida albicans.ConclusionsWe have identified four organotellurides that are promising candidates for the reversal of drug resistance mediated by drug efflux pumps. These molecules will act as scaffolds for the development of more efficient and effective efflux pump inhibitors that can be used in combination therapy with available antifungals.

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