Mechanism of the condensation reaction between 1-aryl- and heteroaryl-1,4-dihydro-3(2H)-isoquinolinones and aldehydes

4-Benzylidene-1-phenyl-1,4-dihydro-3(2H)-isoquinolinone, the intermediary product of the carbonyl condensation reaction between 1-phenyl-1,4-dihydro-3(2H)-isoquinolinone and benzaldehyde, rearranges in the presence of an equivalent quantity of sodium hydride into 4-benzyl-1-phenyl-3(2H)-isoquinolinone. As the possibility of the migration of the hydrogen at C-1 in the form of a proton or a hydrogen atom (radical reaction) was excluded, the mechanism of the rearrangement could be depicted as an intermolecular hydride anion migration. In case of the 1-(4-pyridyl)- and 1-(3-pyridyl)-1,4-dihydro-3(2H)-isoquinolinones, however, the rearrangement can be carried out also in polyphosphoric acid and in this case a proton loss-proton gain mechanism was proved.     

Analysis of cyanobacterial toxins (anatoxin-a, cylindrospermopsin, microcystin-LR) by capillary electrophoresis

Capillary zone electrophoresis (CZE) and micellar electrokinetic chromatography (MEKC) were applied to the simultaneous separation of cyanobacterial toxins (anatoxin-a, microcystin-LR, cylindrospermopsin). The analytical performance data of both methods, optimized for the three toxins, were similar with a precision of migration times smaller than 0.8 RSD% and a detection limit in the range of 1-4 microg/mL, using spectrophotometric detection at 230 nm. Both methods were applied to an analysis of cyanotoxins in water bloom samples and crude cyanobacterial extracts. The results obtained indicate that, for complex matrices, the sequential application of CZE and MEKC is necessary. It is recommended to use both CE techniques for the analysis of the same sample in order to confirm the results by an orthogonal approach.     

Single-isomer sulfated alpha-cyclodextrins for capillary electrophoresis. Part 2. Hexakis(6-O-sulfo)-alpha-cyclodextrin: synthesis, analytical characterization, and initial screening tests

The second member of the family of single-isomer sulfated alpha-cyclodextrins, the sodium salt of hexakis(6-O-sulfo)-alpha-cyclodextrin (HxS), has been synthesized, analytically characterized, and used as the resolving agent for the capillary electrophoretic separation of the enantiomers of nonionic, weak-acid and weak-base analytes present in our initial screening kit. HxS interacted less strongly with many of the analytes tested than the larger-ring analogs, heptakis(6-O-sulfo)-beta-cyclodextrin (HS) and octakis(6-O-sulfo)-gamma-cyclodextrin (OS). For some of the analytes, the separation selectivities obtained with HxS were complementary to those observed with hexakis(2,3-di-O-acetyl-6-O-sulfo)-alpha-cyclodextrin (HxDAS), HS, and OS. For all analytes, the effective mobilities and separation selectivities as a function of the background electrolyte concentration of HxS followed the trends that were found for HxDAS, HS, and OS.     

The mass spectral fragmentation of 1,4-butanediol

The behaviour of 1,4-butanediol under electron impact at 70 and 12.5 eV has been studied with the aid of high resolution mass spectra. Based on metastable ion decompositions and deuterium labelling, mechanisms are proposed for the formation of the abundant ions of this compound.     

Capillary electrophoretic chiral separations using cyclodextrin additives: III. Peak resolution surfaces for ibuprofen and homatropine as a function of the pH and the concentration of β-cyclodextrin

Our recent extended peak resolution equation of capillary electrophoresis has been combined with the multiple equilibria-based electrophoretic mobility model of chiral separations to describe peak resolution as a function of the composition of the background electrolyte (pH and the β-cyclodextrin concentration) and a function of the operating variables (effective portion of the applied potential, dimensionless electroosmotic flow coefficient). Using the previously determined model parameters, the resolution surfaces were calculated for a Type I chiral separation (ibuprofen), and a Type III chiral separation (homatropine). In Type I separations resolution can be obtained only over a narrow pH range in the vicinity of the pK_a value, and above a minimum value, the concentration of β-cyclodextrin plays a lesser role. In Type III separations, the pH- and β-cyclodextrin concentration-dependent resolution surface has two lobes, on which the migration order of the enantiomers is opposite. This can be an advantage in trace component analysis. In both Type I and Type III separations, peak resolution varies strongly with the dimensionless electroosmotic flow coefficient when its value is changed in the − 1 to 1 range. The loci of the pH-dependent and the β-cyclodextrin concentration-dependent resolution maxima do not shift significantly when the dimensionless electroosmotic flow coefficient is changed. This fact provides the analyst with an additional resolution enhancement tool that does not alter the selectivity of the separation. The utility of the model and its theoretical predictions has been demonstrated by comparing measured and calculated R_s values for ibuprofen and homatropine.     

Stereochemical studies, 47, saturated heterocycles, 25 a simple stereospecific synthesis of oxazasteroids

8-Aza-12-oxasteroids have been synthesized in a simple three-step process. As a consequence of two stareocontrolled reactions, the product is a stereospecifically homogeneous isomer with all-$\text{trans}$ ring junctions; its structure has been determined by ¹H and ¹³C NMR spectroscopy and X-ray diffraction.     

Reactions of 2-Deoxy-4, 5-O-Isopropylidene-D-Erythro- and D-Threo-Pent-1-Enose Derivatives

ABSTRACT

The reactivity of the title compounds has been studied toward different nucleophiles and electrophiles. Unlike other ketene dithioacetals, compounds 3-5 did not add nucleophiles to the double bond. Instead, in the presence of Lewis acids they underwent substitution reaction at position 3. If the nucleophile was not strong enough, formation of 6 and 7 were observed. With 2,3,4,6-tetra-O-acetyl-1-thio-β-D-glucopyranose (18), a 3:1 mixture of 11 and 12 was formed from 4. These observations may be interpreted in terms of easy formation of the allylic carbocation I which gives diastereomers with nucleophiles. However, this allylic ether-like behaviour was ruled out by the fact that compounds 9 and 10 did not undergo [2,3] sigmatropic rearrangement with lithium diisopropylamide. With N-bromosuccinimide compound 3 gave the 2-bromo derivative 8. Compounds 3 and 8 resisted common mercury salt assisted demercaptalization procedures.     

Polycapillary‐optics‐based micro‐XANES and micro‐EXAFS at a third‐generation bending‐magnet beamline

A focusing system based on a polycapillary half‐lens optic has been successfully tested for transmission and fluorescence µ‐X‐ray absorption spectroscopy at a third‐generation bending‐magnet beamline equipped with a non‐fixed‐exit Si(111) monochromator. The vertical positional variations of the X‐ray beam owing to the use of a non‐fixed‐exit monochromator were shown to pose only a limited problem by using the polycapillary optic. The expected height variation for an EXAFS scan around the Fe K‐edge is approximately 200 µm on the lens input side and this was reduced to ～1 µm for the focused beam. Beam sizes (FWHM) of 12–16 µm, transmission efficiencies of 25–45% and intensity gain factors, compared with the non‐focused beam, of about 2000 were obtained in the 7–14 keV energy range for an incoming beam of 0.5 × 2 mm (vertical × horizontal). As a practical application, an As K‐edge µ‐XANES study of cucumber root and hypocotyl was performed to determine the As oxidation state in the different plant parts and to identify a possible metabolic conversion by the plant.     

Decoherence within a single atom

An “almost diagonal” reduced density matrix (in coordinate representation) is usually a result of environment induced decherence and is considered the sign of classical behavior. We show that the proton of a ground state hydrogen atom can indeed possess such a density matrix. This example demonstrates that the “almost diagonal” structure may be derived from an interaction with a low number of degrees of freedom which play the role of the environment. We also show that decoherence effects in our example can only be observed if the interaction with the measuring device is significantly faster than the interaction with the environment (the electron). In the opposite case, when the interaction with the environment is significant during the measurement process, coherence is maintained. Finally, we propose a neutron scattering experiment on cold He atoms to observe decoherence which shows up as an additional positive contribution to the differential scattering cross section. This contribution is inversely proportional to the bombarding energy.     

Detection and analysis of cyclotrimethylenetrinitramine (RDX) in environmental samples by surface‐enhanced Raman spectroscopy

Techniques for rapid and sensitive detection of energetics such as cyclotrimethylenetrinitramine (RDX) are needed both for environmental and security screening applications. Here we report the use of surface‐enhanced Raman scattering (SERS) spectroscopy to detect traces of RDX with good sensitivity and reproducibility. Using gold (Au) nanoparticles (∼90–100 nm in diameter) as SERS substrates, RDX was detectable at concentrations as low as 0.15 mg/l in a contaminated groundwater sample. This detection limit is about two orders of magnitude lower than those reported previously using SERS techniques. A surface enhancement factor of ∼6 × 10⁴ was obtained. This research further demonstrates the potential for using SERS as a rapid, in situ field screening tool for energetics detection when coupled with a portable Raman spectrometer. Copyright © 2010 John Wiley & Sons, Ltd.