Isolation of Volatile Compounds with Repellent Properties against Aedes albopictus (Diptera: Culicidae) Using CPC Technology

The present work describes the use of Centrifugal Partition Chromatography (CPC) for the bio-guided isolation of repellent active volatile compounds from essential oils. Five essential oils (EOs) obtained from three Pinus and two Juniperus species were initially analyzed by gas chromatography–mass spectrometry (GC/MS) and evaluated for their repellent properties against Aedes albopictus. The essential oil from needles of P. pinea (PPI) presented the higher activity, showing 82.4% repellency at a dose of 0.2 μL/cm². The above EO, together with the EO from the fruits of J. oxycedrus subsp. deltoides (JOX), were further analyzed by CPC using the biphasic system n-Heptane/ACN/BuOH in ratio 1.6/1.6/0.2 (v/v/v). The analysis of PPI essential oil resulted in the recovery of (−)-limonene, guaiol and simple mixtures of (−)-limonene/β-pheladrene, while the fractionation of JOX EO led to the recovery of β-myrcene, germacrene-D, and mixtures of α-pinene/β-pinene (ratio 70/30) and α-pinene/germacrene D (ratio 65/45). All isolated compounds and recovered mixtures were tested for their repellent activity. From them, (−)-limonene, guaiol, germacrene-D as well the mixtures of (−)-limonene/β-pheladrene presented significant repellent activity (>97% repellency) against Ae. albopictus. The present methodology could be a valuable tool in the effort to develop potent mosquito repellents which are environmentally friendly.     

Nucleation, Growth, and Scaling in Slow Combustion

We study the nucleation and growth of flame fronts in slow combustion. This is modeled by a set of reaction-diffusion equations for the temperature field, coupled to a background of reactants and augmented by a term describing random temperature fluctuations for ignition. We establish connections between this model and the classical theories of nucleation and growth of droplets from a metastable phase. Our results are in good agreement with theoretical predictions.     

Mapping of the cerebral response to acetazolamide using graded asymmetric spin echo EPI

Cerebral vascular reactivity in different regions of the rat brain was quantitatively characterized by spatial and temporal measurements of blood oxygenation level-dependent (BOLD)-fMRI signals following intravenous administration of the carbonic anhydrase inhibitor acetazolamide: this causes cerebral vasodilatation through a cerebral extracellular acidosis that spares neuronal metabolism and vascular smooth muscle function, thus separating vascular and cerebral metabolic events. An asymmetric spin echo-echo planar imaging (ASE-EPI) pulse sequence sensitised images selectively to oxygenation changes in the microvasculature; use of a surface coil receiver enhanced image signal-to-noise ratios (SNRs). Image SNRs and hardware integrity were verified by incorporating quality assurance procedures; cardiorespiratory stability in the physiological preparations were monitored and maintained through the duration of the experiments. These conditions made it possible to apply BOLD contrast fMRI to map regional changes in cerebral perfusion in response to acetazolamide administration. Thus, fMRI findings demonstrated cerebral responses to acetazolamide that directly paralleled the known physiological actions of acetazolamide and whose time courses were similar through all regions of interest, consistent with acetazolamide's initial distribution in brain plasma, where it affects cerebral haemodynamics by acting at cerebral capillary endothelial cells. However, marked variations in the magnitude of the responses suggested relative perfusion deficits in the hippocampus and white matter regions correlating well with their relatively low vascularity and the known vulnerability of the hippocampus to ischaemic damage.     

Carbon nanotube array-based biosensor

Aligned multi-wall carbon nanotubes (MWNT) grown on platinum substrate are used for the development of an amperometric biosensor. The opening and functionalization by oxidation of the nanotube array allows for the efficient immobilization of the model enzyme, glucose oxidase. The carboxylated open-ends of nanotubes are used for the immobilization of the enzymes, while the platinum substrate provides the direct transduction platform for signal monitoring. It is also shown that carbon nanotubes can play a dual role, both as immobilization matrices and as mediators, allowing for the development of a third generation of biosensor systems, with good overall analytical characteristics.     

Structural Characterization of Graphene Nanosheets for Miniaturization of Potentiometric Urea Lipid Film Based Biosensors

The present article describes a miniaturized potentiometric urea lipid film based biosensor on graphene nanosheets. Structural characterization of graphene nanosheets for miniaturization of potentiometric urea lipid film based biosensors have been studied through atomic force microscopy (AFM) and transmission electron microscopy (TEM) measurements. UV‐Vis and Fourrier transform IR (FTIR) spectroscopy have been utilized to study the pre‐ and postconjugated surfaces of graphene nanosheets. The presented potentiometric urea biosensor exhibits good reproducibility, reusability, selectivity, rapid response times (～4 s), long shelf life and high sensitivity of ca. 70 mV/decade over the urea logarithmic concentration range from 1×10^?6 M to 1×10^?3 M.     

Phenalenannulations: Three-Point Double Annulation Reactions that Convert Benzenes into Pyrenes

3-Point annulations, or phenalenannulations, transform a benzene ring directly into a substituted pyrene by “wrapping” two new cycles around the perimeter of the central ring at three consecutive carbon atoms. This efficient, modular, and general method for π-extension opens access to non-symmetric pyrenes and their expanded analogues. Potentially, this approach can convert any aromatic ring bearing a -CH₂Br or a -CHO group into a pyrene moiety. Depending upon the workup choices, the process can be directed towards either tin- or iodo-substituted product formation, giving complementary choices for further various cross-coupling reactions. The two-directional bis-double annulation adds two new polyaromatic extensions with a total of six new aromatic rings at a central core.     

Rhodium(I)‐Catalyzed Decarbonylative Spirocyclization through C?C Bond Cleavage of Benzocyclobutenones: An Efficient Approach to Functionalized Spirocycles

The rhodium‐catalyzed formation of all‐carbon spirocenters involves a decarbonylative coupling of trisubstituted cyclic olefins and benzocyclobutenones through C C activation. The metal–ligand combination [{Rh(CO)₂Cl}₂]/P(C₆F₅)₃ catalyzed this transformation most efficiently. A range of diverse spirocycles were synthesized in good to excellent yields and many sensitive functional groups were tolerated. A mechanistic study supports a hydrogen‐transfer process that occurs through a β‐H elimination/decarbonylation pathway.     

Are metal alkoxides linear owing to electrostatic repulsion?

Density functional theory calculations on [LnCp2APh] (Ln = La, Lu; Cp = eta 5-C5H5; A = O, S; Ph = C6H5) suggest that the linearity of the Ln-O-C vectors arises largely as a result of electrostatic repulsion between the alpha carbon and the trivalent metal centre.     

Characterizing Pressure‐Induced Uranium CH Agostic Bonds

The diuranium(III) compound [UN′′₂]₂(μ‐η⁶:η⁶‐C₆H₆) (N′′=N(SiMe₃)₂) has been studied using variable, high‐pressure single‐crystal X‐ray crystallography, and density functional theory . In this compound, the low‐coordinate metal cations are coupled through π‐ and δ‐symmetric arene overlap and show close metal? CH contacts with the flexible methyl CH groups of the sterically encumbered amido ligands. The metal–metal separation decreases with increasing pressure, but the most significant structural changes are to the close contacts between ligand CH bonds and the U centers. Although the interatomic distances are suggestive of agostic‐type interactions between the U and ligand peripheral CH groups, QTAIM (quantum theory of atoms‐in‐molecules) computational analysis suggests that there is no such interaction at ambient pressure. However, QTAIM and NBO analyses indicate that the interaction becomes agostic at 3.2 GPa.