Formal gas-phase polar [4 + 1+] cycloaddition of ionized methylene to alpha-dicarbonyl compounds: synthesis of 2-unsubstituted 1,3-dioxoles

Ion/molecule reactions of +CH2OCH2. with alpha-dicarbonyl compounds were performed via pentaquadrupole mass spectrometry. Besides the previously known [3+ + 2] 1,3-cycloaddition reaction that forms cyclic 1,3-dioxonium ions, an unprecedented reaction proceeding formally by [4 + 1+] cycloaddition of ionized methylene (CH2+.) to the alpha-dicarbonyl compounds occurs competitively, leading to the gas-phase synthesis of several ionized 2-unsubstituted 1,3-dioxoles. This novel cycloaddition reaction may therefore be added to the set of methods available for the synthesis of 1,3-dioxoles.     

An optical biosensor for dichlovos using stacked sol-gel films containing acetylcholinesterase and a lipophilic chromoionophore

An optical biosensor consisting of a chromoionophore (ETH5294) (CM) doped sol-gel film interfaced with another sol-gel film immobilized with acetylcholinesterase (AChE) was employed to detect the insecticide dichlorvos. The main advantage of this optical biosensor is the use of a sol-gel layer with immobilized CM that possesses lipophilic property. The highly lipophilic nature of the CM and its compatibility with the sol-gel matrix has prevented leaching, which is frequently a problem in optical sensor construction based on pH indicator dyes. The immobilization of the indicator and enzyme was simple and need no chemical modification. The CM layer is pH sensitive and detects the pH changes of the acetylcholine chloride (AChCl) substrate when hydrolyzed by AChE layer deposited above. In the absence of the AChE layer, the pH response of the CM layer is linear from pH 6 to 8 (R² = 0.98, n = 3) and it showed no leaching of the lipophilic chromoionophore. When the AChE layer is deposited on top, the optical biosensor responds to AChCl with a linear dynamic range of 40-90 mM AChCl (R² = 0.984, n = 6). The response time of the biosensor is 12 min. Based on the optimum incubation time of 15 min, a linear calibration curve of dichlorvos against the percentage inhibition of AChE was obtained from 0.5 to 7 mg/L of dichlorvos (17-85% inhibition, R² = 0.991, n = 9). The detection limit for dichlorvos was 0.5 mg/L. The results of the analysis of 1.7-6.0 mg/L of dichlorvos using this optical biosensor agreed well with a gas chromatography-mass spectrometry detection method.     

Photoreactivity of iron(III)-aerobactin: photoproduct structure and iron(III) coordination

UV photolysis of the ferric aerobactin complex results in decarboxylation of the alpha-hydroxy carboxylic acid group of the central citrate moiety of aerobactin. The structure determination of the photooxidized ligand shows that decarboxylation occurs at the citrate moiety forming a 3-ketoglutarate moiety. Proton and carbon-13 NMR establish the presence of keto and enol tautomers of the apo-photoproduct, with the enol form prevailing in water. The photoproduct retains the ability to coordinate iron(III). The values of the ligand protonation constants, the pKa of the Fe(III)-ligand complex, and the Fe(III) stability constant of the photoproduct of aerobactin are all close to those of aerobactin. CD spectroscopy suggests that the chirality of the ferric complexes of aerobactin and its photoproduct are similar. Like aerobactin, the photoproduct promotes iron acquisition by the source bacterium, Vibrio sp. DS40M5.     

Stereoselective Synthesis of Morpholines via Copper-Promoted Oxyamination of Alkenes

A new copper(II) 2-ethylhexanoate-promoted addition of an alcohol and an amine across an alkene (oxyamination) is reported. The alcohol addition is intramolecular, while coupling with the amine occurs intermolecularly. Several 2-aminomethyl morpholines were synthesized in good to excellent yields and diastereoselectivities.     

Phosphatase-triggered fusogenic liposomes for cytoplasmic delivery of cell-impermeable compounds

License to fuse! A phosphorylated fusion peptide can mediate membrane fusion when the phosphates (green triangles, see scheme) are removed by phosphatases (blue spheres), delivering the contents of the liposome into the cytosol. This phosphatase-triggered approach may be useful to create target-specific lipid nanocarriers.     

An operando DRIFTS investigation into the resistance against CO2 poisoning of a Rh/alumina catalyst during toluene hydrogenation

CO(2) is a major contaminant of renewable H(2) derived from biomass fermentation. The effect of the presence of CO(2) on the activity of alumina-supported Pt and Rh catalysts used for the hydrogenation of toluene at 348 K was investigated. The use of operando diffuse reflectance spectroscopy (DRIFTS) was crucial in unravelling the changes in the nature and abundance of species adsorbed at the sample surface and relating those to the changes of catalytic activity. Rhodium supported on alumina was only partly deactivated by the introduction of CO(2) during the hydrogenation of toluene, contrary to the case of Pt/alumina. Rh was only partially covered by carbonyl species derived from CO(2) and it was shown that toluene could successfully compete with some of the linearly adsorbed carbonyls for adsorption. The alumina support stored many CO(2)-derived adsorbates (carbonates, hydrogenocarbonates, carboxylates) that could spill over to the metal and form carbonyl species even after the removal of CO(2) from the feed.     

Glass/PDMS hybrid microfluidic device integrating vertically aligned SWCNTs to ultrasensitive electrochemical determinations

This communication reports a promising platform for rapid, simple, direct, and ultrasensitive determination of serotonin. The method is related to integration of vertically aligned single-walled carbon nanotubes (SWCNTs) in electrochemical microfluidic devices. The required microfabrication protocol is simple and fast. In addition, the nanomaterial influenced remarkably the obtained limit-of-detection (LOD) values. Our system achieved a LOD of 0.2 nmol L(-1) for serotonin, to the best of our knowledge one of the lowest values reported in the literature.     

2.2]Paracyclophane derived bisphosphines for the activation of hydrogen by FLPs: application in domino hydrosilylation/hydrogenation of enones

The heterolytic splitting of hydrogen by two types of [2.2]paracyclophane derived bisphosphines (1, 2a and 2b) in combination with tris(pentafluorophenyl)borane (3) at room temperature is described. The corresponding frustrated Lewis pairs (FLPs) exhibit different behavior in the activation of hydrogen. This results from diverse steric and electronic properties of the bisphosphines. The reactivity of the frustrated Lewis pairs was exploited in the first diastereoselective domino hydrosilylation/hydrogenation reaction catalyzed by FLPs.