Rapid Raman mapping of a fulgurite

A fulgurite is a naturally occurring glass formed when lightning hits sand, rock, or soil. The formation of fulgurites is accompanied by mineralogical and sometimes compositional changes, and may record information about the environment in which they were formed. A previous investigation using Raman point spectroscopy discovered the presence of anatase, a low-temperature polymorph of TiO₂, and polyaromatic hydrocarbons within a fulgurite. These findings indicate that there were regions within the sample that were not subjected to temperatures of 2,000 K or more that the matrix is reported to attain when struck by lightning. This paper seeks to expand the previous research by utilizing the capabilities of a new Raman spectroscopic technological development that enables rapid mapping. The entire surface area of a cross-sectioned fulgurite (∼40 mm × 23 mm) sample was mapped allowing several regions of polyaromatic hydrocarbons and anatase to be located. Furthermore, shocked quartz was found within the boundary regions of the fulgurite, and is proposed to have resulted from contact with vaporized material during the lightning strike. Shocked quartz is typically indicative of extraterrestrial impact, yet its discovery here suggests that its formation is not exclusive to the impact process.     

Microwave-assisted synthesis of symmetric and asymmetric viologens

Viologens are generally synthesized by N-alkylating 4,4′-bipyridine with alkyl halides. Under conventional heating conditions, however, their synthesis suffers from long reaction times and, often, low yields. In this work, symmetric and asymmetric viologens were synthesized under the assistance of microwave irradiation in good to excellent yields and in short reaction times.     

Osmotic and Activity Coefficients of Trimethyloctylammonium Bromide and Decyltrimethylammonium Bromide in Aqueous Solutions as a Function of Temperature

Osmotic coefficients of aqueous solutions of trimethyloctylammonium bromide and decyltrimethylammonium bromide were measured by the isopiestic method at the following temperatures: 298.15, 293.15, 288.15 and 283.15 K. Activity coefficients of the solutes were calculated from the osmotic coefficients. The results were compared with the Debye-Hückel limiting law and analyzed according to their variation with the alkyl chain length of the cation and with the change in temperature.     

Crown ether appended cyclam receptors for cationic guests

A series of crown ether appended macrocyclic amines has been prepared comprising benzo-12-crown-4, benzo-15-crown-5, or benzo-18-crown-6 attached to a diamino-substituted cyclam. The Co(III) complexes of these three receptors have been prepared and characterized spectroscopically and structurally. Crystal structures of each receptor in complex with an alkali metal ion and structures of the benzo-12-crown-4 and benzo-15-crown-5-receptors without guest ions are reported. 2D NMR and molecular mechanics modeling have been used to examine conformational variations upon guest ion complexation. Addition of cations to these receptors results in an appreciable anodic shift in the Co(III/II) redox potential, even in aqueous solution, but little cation selectivity is observed. Evidence for complex formation has been corroborated by (23)Na and (7)Li NMR spectroscopy and electrospray mass spectrometry.     

Two-state folding observed in individual protein molecules

The folding dynamics of small proteins are often described in terms of a simple two-state kinetic model. Within this notion, the behavior of individual molecules is expected to be stochastic, with a protein molecule residing in either the unfolded or the folded state for extended periods of time, with intermittent rapid jumps across the free energy barrier. However, a direct observation of this bistable behavior has not been made to date. Rather, previous reports of folding trajectories of individual proteins have shown an unexpected degree of complexity. This raises the question whether the simple kinetic properties derived from classical experiments on large ensembles of molecules are reflected in the folding paths taken by individual proteins. Here we report single-molecule folding/unfolding trajectories observed by fluorescence resonance energy transfer for a protein that meets all criteria of a two state-system. The trajectories, measured on molecules immobilized in lipid vesicles, demonstrate the anticipated bistable behavior, with steplike transitions between folded and unfolded conformations. They further allow us to put an upper bound on the barrier crossing time.     

Structural phase transition and magnetic properties of the Sr2FeRe1−xBx′O6 (B′=Nb, Ta; x=0, 0.1) double perovskites

The double perovskites, Sr₂FeReO₆ and Sr₂FeRe_0.9M_0.1O₆ (M=Nb, Ta) have been obtained by soft synthesis methods which yield homogeneous particles of micrometric grain size. The materials have been studied by X-ray and neutron powder diffraction, scanning electron microscopy and magnetic measurements. Rietveld refinements show that the compounds adopt a tetragonal I4/mmm structure at high temperatures and monoclinic P2₁/n below the transition temperature. The magnetic structures were determined by neutron powder diffraction at 100 and 300 K for the Sr₂FeReO₆, Sr₂FeRe_0.9Nb_0.1O₆ and Sr₂FeRe_0.9Ta_0.1O₆ phases, respectively. Evidence for a ferrimagnetic coupling between the Fe³⁺ and Re⁵⁺ sublattices has been observed. Magnetic measurements yield magnetic moments lower than the theoretical ones being in accord with the antisite disorder of 25% in the B-B′ positions.     

ZP8, a neuronal zinc sensor with improved dynamic range; imaging zinc in hippocampal slices with two-photon microscopy

The synthesis of a difluorofluorescein monocarboxaldehyde platform and its use for preparing ZP8, a new member of the Zinpyr family of neuronal Zn(2+) sensors, are described. By combining an aniline photoinduced electron transfer (PET) switch and an electron-withdrawing fluorescein scaffold, ZP8 displays reduced background fluorescence and improved dynamic range compared to previous ZP probes. The bright sensor undergoes an 11-fold increase in fluorescence intensity upon Zn(2+) complexation (Phi = 0.03-0.35) with high selectivity over cellular concentrations of Ca(2+) and Mg(2+). In addition, sensors in the ZP family have been utilized for optical imaging in biological samples using two-photon microscopy (TPM). The cell-permeable ZP3 probe is capable of identifying natural pools of labile Zn(2+) within the mossy fiber synapses of live hippocampal slices using TPM, establishing the application of this technique for monitoring endogenous Zn(2+) stores.     

Monitoring coal-tar pitch composition changes during air-blowing by gas chromatography

A series of air-blown coal-tar pitches was studied by GC and GC-MS in order to achieve a deeper understanding of the behaviour of the different pitch components during air-blowing. Compounds present in the parent pitch were identified and quantified and then compared to those present in the air-blown pitches. The compounds observed were identical before and after the treatments, but the concentration of each compound changed with the treatment to a different extent depending on its molecular structure and consequently its reactivity to oxygen. The most reactive compounds were those with a mehylene-bridge in a five member ring, followed by those with a methyl group in their structure.     

Rapid analysis of antimicrobial metabolites monoacetylphloroglucinol and 2,4-diacetylphloroglucinol using capillary zone electrophoresis

A rapid capillary electrophoretic (CE) method was developed for the determination of phloroglucinol compounds, monoacetylphloroglucinol (MAPG) and 2,4-diacetylphloroglucinol (DAPG), in microbial supernatants of Pseudomonas fluorescens F113 over a 24-h growth cycle. Prior to electrophoretic separation, solid-phase extraction of supernatant samples on octadecylsilica for the purpose of sample cleanup is recommended. The optimum electrophoretic conditions were found to be 25 mM sodium tetraborate running buffer at pH 9.3, temperature at 25 degrees C with an applied voltage of 25 kV. The capillary was an Agilent fused-silica capillary of total length 33 cm x 50 microm inner diameter, 375 microm outer diameter, with effective length 24.5 cm. While MAPG and DAPG were monitored at selected wavelengths in the range of 214-320 nm, analysis at 214 nm was used and a CE separation time of less than 2 min was achieved. A partial method validation study was performed in accordance with European Agency for Evaluation of Medicinal Products (EMEA) guidelines. The method displayed linearity over the investigated range of 10-200 microg/mL, with limits of detection of 1.2 microg/mL for MAPG and 1.3 microg/mL for DAPG.