ESR spectrometer with a loop-gap resonator for cw and time resolved studies in a superconducting magnet

The design and performance of an electron spin resonance spectrometer operating at 3 and 9 GHz microwave frequencies combined with a 9-T superconducting magnet are described. The probehead contains a compact two-loop, one gap resonator, and is inside the variable temperature insert of the magnet enabling measurements in the 0-9T magnetic field and 1.5-400 K temperature range. The spectrometer allows studies on systems where resonance occurs at fields far above the g approximately 2 paramagnetic condition such as in antiferromagnets. The low quality factor of the resonator allows time resolved experiments such as, e.g., longitudinally detected ESR. We demonstrate the performance of the spectrometer on the NaNiO2 antiferromagnet, the MgB2 superconductor, and the RbC60 conducting alkaline fulleride polymer.     

Nica’s <Emphasis Type="Italic">q</Emphasis>-Convolution is Not Positivity Preserving

It is shown that the q-convolution of Nica is not positivity preserving unless q=0 or q=1, i.e. the q-convolution of two probability measures with finite moments of all orders is not necessarily a probability measure.Supported by Grant-in-Aid for JSPS Fellows     

Intranasal irradiation with the xenon chloride ultraviolet B laser improves allergic rhinitis

We earlier reported that the 308 nm xenon chloride (XeCl) ultraviolet B (UVB) laser is highly effective for the treatment of inflammatory skin diseases. Since UVB irradiation has been shown to exert both local and systemic immunosuppression, we investigated the clinical efficacy of UVB irradiation in allergic rhinitis. In an open study, groups of patients with severe allergic rhinitis received intranasal irradiation with a 308 nm XeCl UVB excimer laser for two weeks. In the low-dose group (n=10), treatment was given twice weekly, starting with 0.25x the individual minimal erythema dose (MED), whereas patients in the medium-dose group (n=8) were treated four times weekly, starting with 0.4x MED. In each group, the dosage was gradually increased. Evaluation was based on the symptom scores. The effect of the XeCl laser on the skin prick test reaction was also studied. In the low-dose group, seven patients completed the study, and there was no improvement in the nasal symptoms. In the medium-dose group, the XeCl UVB irradiation significantly inhibited the rhinorrhoea, the sneezing, the nasal obstruction and the total nasal score (p<0.05). The XeCl UVB excimer laser also inhibited the allergen-induced skin prick test in a dose-dependent manner. These results suggest that the XeCl UVB excimer laser might serve as a new therapeutic tool in the treatment of allergic rhinitis.     

Angular distributions in the dimuon hadronic production at 150 GeV/c

From π^- interactions at 150 GeV/c on a heavy target, we present the final analysis of the dimuon decay angular distribution in the mass interval 4.5–8.5 GeV/c². Results are presented and discussed in various reference frames and are also given in terms of the density matrix elements. Finally the possible contribution of higher-twist effects at largex ₁ is discussed; we find that our data are not compatible with higher twist contributions as proposed by the Berger and Brodsky Model.     

A DFT study on the vibrational spectroscopy of protoporphyrin IX

Infrared and Raman spectra of protoporphyrin IX were recorded. DFT quantum chemical calculations were performed. Optimised molecular geometry, electric charge distribution, vibrational force constants were computed. The normal coordinate analysis and the scaling of the force constants yielded all the necessary data for the simulation of the infrared and Raman spectra and the potential energy distribution calculations. The result was the interpretation of all vibrational modes of the molecule. Conclusions were drawn from the difficulties arisen during the assignment of the vibrational spectra of such large molecules.     

Electron ionization mass spectra of phosphorus-containing heterocycles. II. 1,2,3,4,4a,5,6,7,8,8a-decahydro-1,3,2-benzodiazaphosphinine 2-oxides

The electron ionization mass spectra of cis- and trans-fused 1,2,3,4,4a,5,6,7,8,8a-decahydro-1,3,2-benzodiazaphosphinine 2-oxides (1-17) were recorded, and the fragmentation pathways were established and compared with those of 1,4,4a,5,6,7,8,8a-octahydro-2H-3,1,2-benzoxazaphosphinine 2-oxides. In general, the mass spectral behaviors of the isomeric compounds were very similar and it was mostly impossible to differentiate them from each other on the basis of the relative abundances of their characteristic fragment ions. The compounds in which R(2) = Ph or OPh exhibited a series of common fragments, e.g. [R(2)H](+), R(2)PONHR(1(3)+), [M-C(3)H(7)](+) and [M-C(4)H(9)](+), the latter two ions being present in the spectra of only two of the derivatives with an N(CH(2)CH(2)Cl)(2) substituent on the P atom. When R(2) = Ph, numerous other alkyl radicals, alkenes and a cycloalkane were also ejected and these compounds also lost NH(2), NH(3), CH(3)N, CH(4)N or CH(3)NH(2). The compounds with an N(CH(2)CH(2)Cl)(2) substituent on the P atom most closely resembled their 3,1,2-O,N,P analogs in respect of the dominant role of this substituent.     

4-Chloro-2-methoxybenzoates of heavy lanthanides(III) and yttrium(III)

4-Chloro-2-methoxybenzoates of heavy lanthanides(III) and yttrium(III) were obtained as mono-, di-, tri-or tetrahydrates with metal to ligand ratio of 1:3 and general formula Ln(C₈H₆ClO₃)₃·nH₂O, where n=1 for Ln=Er, n=2 for Ln=Tb, Dy, Tm, Y, n=3 for Ln=Ho and n=4 for Yb and Lu. The complexes were characterized by elemental analysis, FTIR spectra, TG, DTA and DSC curves, X-ray diffraction and magnetic measurements. The carboxylate group appears to be a symmetrical bidentate chelating ligand. All complexes are polycrystalline compounds. The values of enthalpy, ΔH, of the dehydration process for analysed complexes were also determined. The solubilities of heavy lanthanide(III) 4-chloro-2-methoxybenzoates in water at 293 K are of the order of 10⁻⁴ mol dm⁻³. The magnetic moments were determined over the range of 76–303 K. The results indicate that there is no influence of the ligand field of 4f electrons on lanthanide ions and the metal ligand bonding is mainly electrostatic in nature.     

Enzyme-catalyzed kinetic resolution of N-Boc-trans-3-hydroxy-4-phenylpyrrolidine

The first enzyme-catalyzed kinetic resolution of tert-butyl-3-hydroxy-4-phenylpyrrolidine-1-carboxylate is presented. Enzyme, solvent and temperature optimization resulted in a new resolution method with E = 40 enantioselectivity. The acetate derivative of the (+)-(3S,4R) enantiomer formed while the (?)-(3R,4S) isomer remained intact. Very good enantioselectivities (E > 200) were achieved in the enzyme-catalyzed alcoholysis of the racemic acetate in i-propanol and t-butanol where the (+)-(3S,4R) enantiomer was prepared in pure form (ee > 99.7%). Absolute configuration of the (?)-(3R,4S)-enantiomer was determined by single crystal X-ray diffraction method.      

Anomalous small angle x-ray scattering determination of ion distribution around a polyelectrolyte biopolymer in salt solution

The distribution of counterions in solutions of high molecular mass hyaluronic acid, in near-physiological conditions where mono- and divalent ions are simultaneously present, is studied by small angle neutron scattering and anomalous small angle x-ray scattering. The solutions contain either sodium or rubidium chloride together with varying concentrations of calcium or strontium chloride. The effects of monovalent-divalent ion exchange dominate the amplitude and the form of the counterion cloud. In the absence of divalent ions, the shape of the anomalous scattering signal from the monovalent ions is consistent with the distribution calculated from the Poisson-Boltzmann equation, as found by other workers. In mixtures of monovalent and divalent ions, however, as the divalent ion concentration increases, both the diameter and the amplitude of the monovalent ion cloud decrease. The divalent counterions always occupy the immediate neighborhood of the charged polyanion. Above a given concentration their anomalous scattering signal saturates. Even in a large excess of divalent ions, ion exchange is incomplete.