Organic reactions mediated by electrochemically generated ArS+

Low-temperature electrochemical oxidation of ArSSAr was carried out to generate a pool of "ArS(+)". Spectroscopic studies ((1)H NMR and CSI-MS) of the resulting solution revealed the accumulation of ArS(ArSSAr)(+). The resulting "ArS(+)" pool reacted with alkenes and alkynes to give diarylthio-substituted products. The "ArS(+)" pool rapidly reacted with thioacetals to give the corresponding alkoxycarbenium ion pools, which reacted with various carbon nucleophiles (indirect cation pool method). The reaction of the alkoxycarbenium ion pools with stilbene derivatives in the presence of ArSSAr gave thiochroman derivatives. In addition to such stoichiometric reactions, a catalytic amount of "ArS(+)" serves as an initiator and a chain carrier of some cationic chain reactions involving intramolecular carbon-carbon bond formation. In situ generation of "ArS(+)" by electrochemical oxidation of ArSSAr with a catalytic amount of electricity in the presence of a substrate is also effective for such cationic chain reactions.     

Effect of co-adsorbed CO and reaction temperature on the dynamics of N2 desorption under steady-state N2O-CO reaction on Rh(110)

We have investigated the effect of co-absorbed CO and reaction temperature on the angular distribution of N(2) desorption by N(2)O decomposition under the steady state of N(2)O-CO reaction on Rh(110). Spatial distributions of desorbing product N(2) emission have been measured at various surface temperatures and CO coverages. The decomposed N(2) collimates at 48°-61° off normal in the parallel plane to [001] and [110] directions, indicating that adsorbed N(2)O just before the decomposition is oriented along the [001] direction. Although the inclined and collimated N(2) desorption is always observed at any steady-state CO coverage and reaction temperature, the shape of the collimated N(2) distribution varied dependent on the co-adsorbed CO coverage. The distribution becomes sharp and shifts toward the surface normal direction with increasing CO coverage. These effects of adsorbed CO on the angular distribution of N(2) are interpreted by the collision of desorbed N(2) with co-adsorbed CO.     

Oxidation of annelated diarylamines: analysis of reaction pathways to nitroxide diradical and spirocyclic products

Oxidation of diaryldiamine 2, a tetrahydrodiazapentacene derivative, provides diarylnitroxide diradical 1 accompanied by an intermediate nitroxide monoradical and a multitude of isolable diamagnetic products. DFT-computed tensors for EPR spectra and paramagnetic (1)H NMR isotropic shifts for nitroxide diradical 1 show good agreement with the experimental EPR spectra in rigid matrices and paramagnetic (1)H NMR spectra in solution, respectively. Examination of the diamagnetic products elucidates their formation via distinct pathways involving C-O bond-forming reactions, including Baeyer-Villiger-type oxidations. An unusual diiminoketone structure and two spirocyclic structures of the predominant diamagnetic products are confirmed by either X-ray crystallography or correlations between DFT-computed and experimental spectroscopic data such as (1)H, (13)C, and (15)N NMR chemical shifts and electronic absorption spectra.     

Stereochemically controlled asymmetric 1,2-reduction of enones mediated by a chiral sulfoxide moiety and a lanthanum(III) ion

Enantiomerically pure (Z)-β-sulfinyl allylic alcohols of either handedness can be readily prepared from (Z)-β-sulfinyl enones using NaBH(4) or DIBAL reductants in the presence of LaCl(3) as a chelating agent. A chiral sulfoxide auxiliary induces the remote 1,2-asymmetric reduction (1,4-induction) to afford various chiral allylic alcohols in high yields with excellent stereoselectivities (up to 100% de).     

The flow field near the triple point in steady shock reflection

This paper investigates the flow field near three intersecting shock waves appearing in steady Mach reflection. Results of numerical computations reveal a “von Neumann Paradox”—like feature for weak shock waves, in which the flow field between the reflected and the Mach stem is smooth with no distinct slip flow region and changes rather smoothly. An analytical solution of the Navier–Stokes equations constructed using a polar–coordinate system gives a flow field with the same properties as the numerical simulation.     

Prediction error criterion for selecting variables in a linear regression model

Several criteria, such as CV, C _p , AIC, CAIC, and MAIC, are used for selecting variables in linear regression models. It might be noted that C _p has been proposed as an estimator of the expected standardized prediction error, although the target risk function of CV might be regarded as the expected prediction error R _PE. On the other hand, the target risk function of AIC, CAIC, and MAIC is the expected log-predictive likelihood. In this paper, we propose a prediction error criterion, PE, which is an estimator of the expected prediction error R _PE. Consequently, it is also a competitor of CV. Results of this study show that PE is an unbiased estimator when the true model is contained in the full model. The property is shown without the assumption of normality. In fact, PE is demonstrated as more faithful for its risk function than CV. The prediction error criterion PE is extended to the multivariate case. Furthermore, using simulations, we examine some peculiarities of all these criteria.     

Synthesis of a calix[4]crown modified with germanium‐containing side chains

A germacalix‐crown, 25,27‐bis[1‐(3‐trimethylgermylpropyl)oxy]calix[4]arene‐crown‐6, 1,3‐alternate ( 1a ), and its carbon analog, 25,27‐bis‐[1‐(4,4‐dimethylpentyl)oxy]calix[4]arene‐crown‐6, 1,3‐alternate ( 1b ), were prepared and their structures were confirmed by elemental analysis and ¹H and ¹³C NMR spectroscopy. A cation transport test indicated that both compounds exhibited much the same cation transport ability, so that the role of the germanium moiety in capturing and transporting counteranions is not yet clear. Copyright © 2005 John Wiley & Sons, Ltd.     

Grazing-exit and micro X-ray fluorescence analyses for chemical microchips.

Grazing-exit x-ray fluorescence (GE-XRF) and micro x-ray fluorescence (micro-XRF) methods were applied to chemical microchips as a detection method. Since an energy-dispersive x-ray detector was used, the simultaneous detection of multiple elements was possible. An analyzing region was especially designed on the microchip so that a sample solution could be dried and concentrated in a suitable area corresponding to the size of the primary x-ray beam. Finally, it was confirmed that both analytical methods could be combined well for use with a microchip. In GE-XRF, the background intensity in the XRF spectrum was reduced at grazing-exit angles. In addition, a good relationship between the x-ray fluorescence intensities and the concentrations of standard solutions that were introduced into the microchip was obtained. This indicates that the GE-XRF method is feasible for trace elemental analysis in chemical microchip systems. In micro-XRF, an attempt was made to concentrate and dry the analyte within a small analyzing region. The preliminary results indicated that the micro-XRF method could be applied for the analysis of microchips.     

Inelastic scattering on 12Be and disappearance of the N = 8 magic number

Experimental studies on in-beam γ-ray spectroscopy using a ¹²Be radioactive beam are presented. Inelastic scattering of the neutron-rich ¹²Be nucleus on ²⁰⁸Pb, ¹²C, and (CH₂)_n targets has been studied by measuring de-excitation γ-rays in coincidence with scattered particles. The level schemes and transition probabilities are determined for low-lying excited states in ¹²Be. The present paper presents a brief review of the spectroscopic results, which may be associated with the N = 8 shell quenching near the drip line. Received: 1 May 2001 / Accepted: 4 December 2001     

Recent research using the Oxford electron beam ion trap

The presence of the σ-phase in Fe-Cr alloys (eg. Stainless steel) is important in industrial applications and from an academic point of view. The presence of the σ-phase in these alloys drastically affects their mechanical properties and their resistance to various corrosive media. In the present investigation Fe-Cr alloys containing different amounts of Mo were prepared and the transformation to the σ-phase was carried out by isothermally annealing the samples for various periods in an argon atmosphere. It will be shown that the presence of Mo has a dramatic accelerating effect on the rate of the σ-phase formation in these alloys. This revised version was published online in August 2006 with corrections to the Cover Date.