2-Acylamino-6-pyridones: breaking of an intramolecular hydrogen bond by self-association and complexation with double and triple hydrogen bonding counterparts. Uncommon steric effect on intermolecular interactions

2-Acylamino-6-pyridones (acyl = RCO, where R = Me, Et, i-Pr, t-Bu, and 1-adamantyl) were previously characterized by X-ray diffractometry and solid-state NMR techniques by us. One of these compounds was used recently in organocatalysis. The series is now studied in solution and by computational methods recommended for noncovalent interactions (DFT/M05). These compounds showed interesting behavior during dilution and titration experiments monitored by (1)H NMR. 2-Acylamino-6-pyridones change their conformation at higher concentrations, forming double hydrogen-bonded dimers and trimers in which an uncommon steric effect is observed. To the best of our knowledge, this is the first example of such behavior of hydrogen-bonded molecules. Heterocomplexation of the studied compounds happens via double or triple hydrogen bonding, depending on the properties of the counterpart. The computation data support and explain the effects observed experimentally, including the tautomeric, closed/open form equilibrium and intermolecular interaction preferences.     

Approaches to the enantioselective synthesis of ferrugine and its analogues

A four-step synthetic route, to ferrugine (2α-benzoyltropane), its methyl analogue (2-acetyltropane) and their N-benzyl analogues is reported. The reaction sequence uses tropinone or N-benzylnortropinone aldols as key intermediates. Reduction of aldol derived N-tosylhydrazones and oxidation of the side chain hydroxyl group followed by spontaneous diastereomer equilibration provides the final products. Relative configuration of the exo,anti N-methyl and N-benzyl aldols was retained during N-tosylhydrazone formation. The relative stereochemistry of N-tosylhydrazones was assigned by single crystal diffraction. The final products, ferrugine and its methyl analogue, were synthesized in enantiomerically pure form via asymmetric deprotonation of tropinone using chiral lithium amide/lithium chloride aggregate prepared in situ from (S,S)-N,N-bis(1-phenylethyl)amine hydrochloride.     

The impact of solvent polarity on intramolecular proton and electron transfer in 2-alkylamino-4-nitro-5-methyl pyridine N-oxides

The crystal structure of 2-butylamino-4-nitro-5-methyl pyridine N-oxide (2B5M) and solution studies of both 2B5M and 2-methylamino-4-nitro-5-methyl pyridine (2M5M) N-oxide are presented. Steady-state absorption and emission measurements were employed for both molecules while a picosecond fluorescence up-conversion technique was used to follow the dynamic behavior of the 2M5M system. The experimental methods were complemented by DFT and TD DFT B3LYP/6-31G(d,p) calculations involving ground and excited-state optimization which in the case of the smaller 2M5M molecule were extended to the CAM-B3LYP/6-31G(d,p) method. The solvent effect is incorporated by applying the polarizable continuum (PCM) model. The data reveal that the 2B5M molecule crystallizes in the monoclinic space group P2(1)/c and its crystal lattice is composed of monomers with intramolecular N-H···O [2.572(3) ?] hydrogen bonds, connected into a polymer network by weak intermolecular C-H…O [3.2-3.4 ?]-type interactions. Quantum-chemical calculations show that the aminoalkyl substitutent in aminoalkyl-pyridine N-oxides is a specific determinant of the CT nature of the lowest-lying excited electronic ππ* state, distinguishing them from other nitroaromatic compounds. The results of both picosecond fluorescence up-conversion experiments in different solvents and quantum-chemical calculations suggest that in nonpolar media the ESIPT process in 2M5M is favored, while in polar acetonitrile, the N* → PT* transition demands barrier-crossing and thus unfavorable thermodynamic conditions do not allow the ESIPT to occur. The signals of picosecond fluorescence up-conversion of 2M5M are solvent- and emission-wavelength dependent. The three time components found in a weakly polar isooctane-dioxane mixture have been attributed to solvation dynamics (～500 fs), and to relaxation of N* and PT* forms while in acetonitrile, a very rapid fluorescence decay with a time constant (2.3-4.0 ps) indicative of the presence of the normal (N*) form was observed. Much shorter fluorescence lifetimes in alcohols (a few picoseconds) and in D(2)O (less than 200 fs) than in aprotic solvents suggest that in protic media, the solvent molecules participate in the ESIPT, bridging between the methylamine group and the N-oxide group of 2M5M.     

Phosphine oxide functionalised imidazolium ionic liquids as tuneable ligands for lanthanide complexation

A series of novel, phosphine oxide functionalised ionic liquids have been synthesised and their application as tuneable lanthanide complexing agents is demonstrated.     

Spin Hall effect and spin current generation in two-dimensional systems with random Rashba spin–orbit coupling

We consider a new effect induced by spin–orbit coupling in a two-dimensional electron gas confined in a semiconductor quantum well, i.e. the possibility of spin current generation by fluctuating random Rashba spin–orbit interaction, with the corresponding mean value of the interaction being equal to zero. Our main results suggest that – in contrast to the spatially uniform Rashba spin–orbit interaction – the spin Hall effect does not vanish for typical disorder strengths. We also point out some other possibilities of using such a random Rashba coupling for the generation of spin density and spin current in two-dimensional nonmagnetic structures.     

A psychophysical pitch function determined by absolute magnitude estimation and its relation to the musical pitch scale

A psychophysical pitch function, describing the relation of perceived magnitude of pitch to the frequency of a pure tone, was determined by absolute magnitude estimation. Pitch estimates were made by listeners with relative pitch and by absolute pitch possessors for 27 tones spanning a frequency range of 31.5-12,500 Hz in 1/3 octave steps. Results show that the pitch function, plotted in log-log coordinates, is steeper below 200 Hz than at higher frequencies. It is hypothesized that the pitch function's bend may reflect the diversity of neurophysiological mechanisms of pitch encoding in frequency ranges below and above 200 Hz. The variation of the function's slope implies that pitch distances between tones with the same frequency ratios are perceived as larger below 200 Hz than at higher frequencies. It is argued that this implication may apply only to a purely sensory concept of pitch distance and cannot be extended to the perception of musical intervals, a phenomenon governed by musical cognitive principles. The results also show that pitch functions obtained for listeners with relative and absolute pitch have a similar shape, which means that quantitative pitch relations determined for both groups of listeners do not differ appreciably along the frequency scale.     

A RVE-based micro mechanical model for short fiber reinforced plastic materials including matrix damage and fiber fracture

The representative volume element (RVE) method is applied to a fiber reinforced polymer material undergoing matrix damage and fiber fracture. Results of RVE computations are compared to uniaxial tensile tests performed with the composite material. It is shown that the macroscopic behavior of the composite material can accurately be predicted by RVE computations. (© 2011 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim)     

Oil refinery dusts: morphological and size analysis by TEM

The objectives of this work were to develop a means of sampling atmospheric dusts on the premises of an oil refinery for electron microscopic study to carry out preliminary morphological analyses and to compare these dusts with those collected at sites beyond the refinery limits. Carbon and collodion membranes were used as a support for collection of dust particles straight on transmission electron microscopy (TEM) grids. Micrographs of the dust particles were taken at magnifications from ×4,000 to ×80,000 with a Tesla BS500 transmission electron microscope. Four parameters were defined on the basis of the micrographs: surface area, Feret diameter, circumference, and shape coefficient. The micrographs and literature data were used to classify the atmospheric dusts into six groups: particles with an irregular shape and rounded edges; particles with an irregular shape and sharp edges; soot and its aggregates; spherical particles; singly occurring, ultrafine dust particles; and particles not allocated to any of the previous five groups. The types of dusts found in all the samples were similar, although differences did exist between the various morphological parameters. Dust particles with the largest Feret diameter were present in sample 3 (mean, 0.739 μm)—these were collected near the refinery's effluent treatment plant. The particles with the smallest diameter were found in the sample that had been intended to be a reference sample for the remaining results (mean, 0.326 μm). The dust particles collected in the refinery had larger mean Feret diameters, even 100% larger, than those collected beyond it. Particles with diameters from 0.1 to 0.2 μm made up the most numerous group in all the samples collected in the refinery.     

Analysis of airborne metal containing particles with EDX/EDS detectors in electron microscopes

In years 2006–2010 particulate matter analysis was undertaken for dust samples collected from Gdansk and London area in order to compare their morphology and composition. Part of those studies was devoted to analysis of particulate matter (PM) bearing metals. Characterization of the morphology and size of the particles collected onto the filters was performed using a scanning electron microscope (SEM) and transmission electron microscope (TEM). Both electron microscopes were equipped with energy dispersive X-ray spectrometers to identify the elemental composition of the particles. On analysis of the X-ray spectra acquired by both TEM and SEM, the particles were divided into 10 groups as follows: Al-rich, Ba-rich, C-rich, Ca-rich, Cl-rich, Fe-rich, Mg-rich, Na-rich, S-rich, Si-rich. Speciation of the particles based on the major element and accompanying minor elements yielded 34 particle types. However, some pairs of elements repeat, for instance: Na-Cl and Cl-Na, Al-S and S-Al, Si-Al and Al-Si, S-Ca and Ca-S. These are undoubtedly the same types of particles; variation in peak heights of the major and minor elements is normal in a mixed particle population.     

Structure and NMR spectra of some [2.2]paracyclophanes. The dilemma of [2.2]paracyclophane symmetry

Density functional theory (DFT) quantum chemical calculations of the structure and NMR parameters for highly strained hydrocarbon [2.2]paracyclophane 1 and its three derivatives are presented. The calculated NMR parameters are compared with the experimental ones. By least-squares fitting of the (1)H spectra, almost all J(HH) coupling constants could be obtained with high accuracy. Theoretical vicinal J(HH) couplings in the aliphatic bridges, calculated using different basis sets (6-311G(d,p), and Huz-IV) reproduce the experimental values with essentially the same root-mean-square (rms) error of about 1.3 Hz, regardless of the basis set used. These discrepancies could be in part due to a considerable impact of rovibrational effects on the observed J(HH) couplings, since the latter show a measurable dependence on temperature. Because of the lasting literature controversies concerning the symmetry of parent compound 1, D(2h) versus D(2), a critical analysis of the relevant literature data is carried out. The symmetry issue is prone to confusion because, according to some literature claims, the two hypothetical enantiomeric D(2) structures of 1 could be separated by a very low energy barrier that would explain the occurrence of rovibrational effects on the observed vicinal J(HH) couplings. However, the D(2h) symmetry of 1 with a flat energy minimum could also account for these effects.