A combined crossed molecular beam and quasiclassical trajectory study of the Titan-relevant N(2D) + D2O reaction

Following a recent investigation on the N(²D) + H₂O reaction [Homayoon et al., J. Phys. Chem. Lett. 5, 3508 (2014)], we report on an experimental and theoretical study of the isotopologue N(²D) + D₂O reaction. Crossed molecular beam (CMB) experiments were conducted at a collision energy of 10.3 kcal mol^–1. Quasiclassical trajectory calculations were performed on a recent potential energy surface to derive the centre-of-mass functions necessary to simulate the CMB laboratory distributions. Excellent agreement was found. The importance of the channel leading to HON/DON was confirmed. The inclusion of this channel, in addition to that leading to the isomer HNO/DNO, can affect the models considering the coupling between nitrogen and oxygen chemistry in the upper atmosphere of Titan.     

Synthesis and Characterization of Triphenylphosphine Oxide-Containing Poly(Aryl Imide)-Poly(Dimethyl Siloxane) Randomly Segmented Copolymers

Abstract

Poly(aryl imide)-poly(dimethyl siloxane) randomly segmented copolymers were synthesized by essentially a one-step solution imidization process in a solvent system consisting of predominately o-dichlorobenzene with a small amount of n-methylpyrolidone. This solvent combination was selected because of its ability to afford homogeneous solutions throughout the polymerization process. This enabled copolymers of any desired poly(dimethyl siloxane) composition to be prepared. A hydrolytically stable triphenylphosphine oxide containing diamine, bis(3-amino-phenoxy-4′-phenyl)phenylphosphine oxide, was utilized as a chain extender and together with oxydiphthalic anhydride formed the hard segment in these copolymers. The soft segment was formed from α,ω-aminopropyl poly(dimethyl siloxane) oligomers of controlled molecular weight. The presence of phosphorus and silicon contributes several unique properties to the system, including enhanced solubility, thermal stability, and flame resistance. High molecular weight copolymers containing up to 60% (w/w) of the poly(dimethyl siloxane) segments were successfully prepared using this method. Gel permeation chromatography analysis, based on a universal calibration curve in CHCl₃, was performed to determine the molecular weights and distribution. These copolymers with 40-60% (w/w) poly(dimethyl siloxane) exhibited upper T_g values ranging from 130 to 180°C and showed substantial char yields at 750°C in air, which increased with siloxane content. Dynamic mechanical analysis confirmed the anticipated microphase behavior by the presence of two separate glass-transition regions. Both small angle x-ray scattering and transmission electron microscopy measurements determined on well-characterized transparent cast films were used to better demonstrate the multiphase nature of these copolymers.     

Detection and identification of the designer benzodiazepine flubromazepam and preliminary data on its metabolism and pharmacokinetics

The appearance of pyrazolam in Internet shops selling ‘research chemicals’ in 2012 marked the beginning of designer benzodiazepines being sold as recreational drugs or ‘self medication’. With recent changes in national narcotics laws in many countries, where two uncontrolled benzodiazepines (phenazepam and etizolam), which were marketed by pharmaceutical companies in some countries, were scheduled, clandestine laboratories seem to turn to poorly characterized research drug candidates as legal substitutes. Following the appearance of pyrazolam, it comes with no surprise that recently, flubromazepam (7‐bromo‐5‐(2‐fluorophenyl)‐1,3‐dihydro‐2H‐1,4‐benzodiazepin‐2‐one), a second designer benzodiazepine, was offered on the market. In this article, this new compound was characterized using nuclear magnetic resonance, gas chromatography‐mass spectrometry (GC–MS), liquid chromatography–mass spectrometry (LC–MS/MS) and liquid chromatography quadrupole time‐of‐flight MS (LC–Q–ToF–MS). Additionally, a study was carried out, in which one of the authors consumed 4 mg of flubromazepam to gain preliminary data on the pharmacokinetic properties and the metabolism of this compound. For this purpose, serum as well as urine samples were collected for up to 31 days post‐ingestion and analyzed applying LC–MS/MS and LC–Q‐ToF‐MS techniques. On the basis of this study, flubromazepam appears to have an extremely long elimination half‐life of more than 100 h. One monohydroxylated compound and the debrominated compound could be identified as the predominant metabolites, the first allowing a detection of a consumption for up to 28 days post‐ingestion when analyzing urine samples in our case. Additionally, various immunochemical assays were evaluated, showing that the cross‐reactivity of the used assay seems not to be sufficient for safe detection of the applied dose in urine samples, bearing the risk that it could be misused in drug‐withdrawal settings or in other circumstances requiring regular drug testing. Furthermore, it may be used in drug‐facilitated crimes without being detected. Copyright © 2013 John Wiley & Sons, Ltd.     

Electrochemical Characterization of Egyptian Blue Pigment in Wall Paintings Using the Voltammetry of Microparticles Methodology

The solid state voltammetric response of Egypt blue, Han blue and ploss blue pigments upon attachment to graphite electrodes in contact with aqueous phosphate buffer at pH 7.0 is studied by voltammetry of microparticles and scanning electrochemical microscopy. Such voltammetric responses, combined with those for synthetic specimens consisting of binary mixtures of the pigment and SiO₂ or CaCO₃ as well as ternary ones of CaCO₃ and SiO₂ mixtures allow for the identification of the pigment and the support in samples from wall paintings using different electrochemical parameters, in particular upon performing the Tafel and modified Tafel analysis of voltammetric peaks. Identification of Egypt blue in microsamples of murals from a Roman archaeological site in Castulo (Jaén, Spain) is discussed.     

Theoretic study of the electronic spectra of neutral and cationic PaO and PaO2

The electronic spectra of neutral PaO and PaO₂ and their mono- (PaO⁺, PaO₂ ⁺) and dications (PaO²⁺, PaO₂ ²⁺) were studied by performing multiconfigurational quantum chemical calculations at the CASSCF/CASPT2 level of theory taking into account spin–orbit coupling. Including the protactinium 7s, 6d, and 5f orbitals as well as selected orbitals of oxygen in the active space, the vertical excitation energies at the ground-state geometries have been computed up to ca. 36,000 cm^?1. The gas-phase electronic spectra at 298 and 3,000 K were evaluated on the basis of the computed oscillator strengths.     

An automated headspace solid-phase microextraction followed by gas chromatography–mass spectrometry method to determine macrocyclic musk fragrances in wastewater samples

A fully automated method has been developed for determining eight macrocyclic musk fragrances in wastewater samples. The method is based on headspace solid-phase microextraction (HS-SPME) followed by gas chromatography–mass spectrometry (GC-MS). Five different fibres (PDMS 7 μm, PDMS 30 μm, PDMS 100 μm, PDMS/DVB 65 μm and PA 85 μm) were tested. The best conditions were achieved when a PDMS/DVB 65 μm fibre was exposed for 45 min in the headspace of 10 mL water samples at 100 °C. Method detection limits were found in the low ng L^?1 range between 0.75 and 5 ng L^?1 depending on the target analytes. Moreover, under optimized conditions, the method gave good levels of intra-day and inter-day repeatabilities in wastewater samples with relative standard deviations (n?=?5, 1,000 ng L^?1) less than 9 and 14 %, respectively. The applicability of the method was tested with influent and effluent urban wastewater samples from different wastewater treatment plants (WWTPs). The analysis of influent urban wastewater revealed the presence of most of the target macrocyclic musks with, most notably, the maximum concentration of ambrettolide being obtained in WWTP A (4.36 μg L^?1) and WWTP B (12.29 μg L^?1), respectively. The analysis of effluent urban wastewater showed a decrease in target analyte concentrations, with exaltone and ambrettolide being the most abundant compounds with concentrations varying between below method quantification limit (<MQL) and 2.46 μg L^?1.

Electrochemical detection of miRNA-222 by use of a magnetic bead-based bioassay

MicroRNAs (miRNAs, miRs) are naturally occurring small RNAs (approximately 22 nucleotides in length) that have critical functions in a variety of biological processes, including tumorigenesis. They are an important target for detection technology for future medical diagnostics. In this paper we report an electrochemical method for miRNA detection based on paramagnetic beads and enzyme amplification. In particular, miR 222 was chosen as model sequence, because of its involvement in brain, lung, and liver cancers. The proposed bioassay is based on biotinylated DNA capture probes immobilized on streptavidin-coated paramagnetic beads. Total RNA was extracted from the cell sample, enriched for small RNA, biotinylated, and then hybridized with the capture probe on the beads. The beads were then incubated with streptavidin–alkaline phosphatase and exposed to the appropriate enzymatic substrate. The product of the enzymatic reaction was electrochemically monitored. The assay was finally tested with a compact microfluidic device which enables multiplexed analysis of eight different samples with a detection limit of 7 pmol L^?1 and RSD?=?15 %. RNA samples from non-small-cell lung cancer and glioblastoma cell lines were also analyzed.