Systematics of Mössbauer parameters in Fe57-doped titanate and germanate ilmenites

The Mössbauer spectra of ilmenite (FeTiO₃), Fe²⁺-doped ilmenites, MTiO₃ (M = Cd, Mn, Zn, Co, Mg and Ni) and MGeO₃ (M = Mn, Zn and Mg), have been studied from 4.2 K to room temperature. Systematic variations in the isomer shift and quadrupole splitting at room temperature are correlated with the change in ionic radii of the host M ions and the c/a ratio of the host crystal, respectively. The quadrupole splittings show a remarkable temperature variation; the magnetic ilmenites show either a sudden increase or a sudden decrease of quadrupole splittings below the Néel temperature, depending on the orientation of the spin axis with respect to the c axis.     

Synthetic studies on chartelline C: stereoselective construction of the core skeleton

What a core-ker! The title synthesis was achieved using a route featuring an intramolecular Mitsunobu reaction of a nosyl amide, stereoselective construction of the β-lactam, and formation of an enamide moiety by selenoxide elimination. The stereochemistry of the alkylation for the formation of the β-lactam was controlled by a secondary hydroxy group on the ten-membered ring. SEM=2-(trimethylsilyl)ethoxymethyl; TBS=tert-butyldimethylsilyl.     

First principles study of sulfuric acid anion adsorption on a Pt(111) electrode

A first principles theory combined with a continuum electrolyte theory is applied to adsorption of sulfuric acid anions on Pt(111) in 0.1 M H(2)SO(4) solution. The theoretical free energy diagram indicates that sulfuric acid anions adsorb as bisulfate in the potential range of 0.41 < U ≤ 0.48 V (RHE) and as sulfate in 0.48 V (RHE) < U. This diagram also indicates that sulfate inhibits formations of surface oxide and hydroxide. Charge analysis shows that the total charge transferred for the formation of the full coverage sulfate adlayer is 90 μC cm(-2), and that the electrosorption valency value is -0.45 to -0.95 in 0.41 < U ≤ 0.48 V (RHE) and -1.75 to -1.85 in U > 0.48 V (RHE) in good agreement with experiments reported in the literature. Vibration analysis indicates that the vibration frequencies observed experimentally at 1250 and 950 cm(-1) can be assigned, respectively, to the S-O (uncoordinated) and symmetric S-O stretching modes for sulfate, and that the higher frequency mode has a larger potential-dependence (58 cm(-1) V(-1)) than the lower one.     

Proton-promoted oxygen atom transfer vs proton-coupled electron transfer of a non-heme iron(IV)-oxo complex

Sulfoxidation of thioanisoles by a non-heme iron(IV)-oxo complex, [(N4Py)Fe(IV)(O)](2+) (N4Py = N,N-bis(2-pyridylmethyl)-N-bis(2-pyridyl)methylamine), was remarkably enhanced by perchloric acid (70% HClO(4)). The observed second-order rate constant (k(obs)) of sulfoxidation of thioaniosoles by [(N4Py)Fe(IV)(O)](2+) increases linearly with increasing concentration of HClO(4) (70%) in acetonitrile (MeCN)at 298 K. In contrast to sulfoxidation of thioanisoles by [(N4Py)Fe(IV)(O)](2+), the observed second-order rate constant (k(et)) of electron transfer from one-electron reductants such as [Fe(II)(Me(2)bpy)(3)](2+) (Me(2)bpy = 4,4-dimehtyl-2,2'-bipyridine) to [(N4Py)Fe(IV)(O)](2+) increases with increasing concentration of HClO(4), exhibiting second-order dependence on HClO(4) concentration. This indicates that the proton-coupled electron transfer (PCET) involves two protons associated with electron transfer from [Fe(II)(Me(2)bpy)(3)](2+) to [(N4Py)Fe(IV)(O)](2+) to yield [Fe(III)(Me(2)bpy)(3)](3+) and [(N4Py)Fe(III)(OH(2))](3+). The one-electron reduction potential (E(red)) of [(N4Py)Fe(IV)(O)](2+) in the presence of 10 mM HClO(4) (70%) in MeCN is determined to be 1.43 V vs SCE. A plot of E(red) vs log[HClO(4)] also indicates involvement of two protons in the PCET reduction of [(N4Py)Fe(IV)(O)](2+). The PCET driving force dependence of log k(et) is fitted in light of the Marcus theory of outer-sphere electron transfer to afford the reorganization of PCET (λ = 2.74 eV). The comparison of the k(obs) values of acid-promoted sulfoxidation of thioanisoles by [(N4Py)Fe(IV)(O)](2+) with the k(et) values of PCET from one-electron reductants to [(N4Py)Fe(IV)(O)](2+) at the same PCET driving force reveals that the acid-promoted sulfoxidation proceeds by one-step oxygen atom transfer from [(N4Py)Fe(IV)(O)](2+) to thioanisoles rather than outer-sphere PCET.     

Ultrashort pulse generation using fiber FM laser

Ultrashort optical pulse generation using a fiber FM laser is presented and analyzed in detail. Fiber FM laser operation is realized using a fiber ring with an internal phase modulator and an erbium-doped fiber amplifier. To compress FM laser pulses, an external dispersive single-mode fiber is employed. Furthermore, by external intensity modulation, the pulse background is removed. The background ratio of the generated ultrashort pulse is calculated and compared with the experimental results. The experimental results show an output optical pulse width of 1.77 ps and a spectral bandwidth of 0.5 THz.     

Sampling Moiré Method for Accurate Small Deformation Distribution Measurement

In this paper, a novel accurate deformation distribution measurement technique by using sampling moiré method is proposed. The basic principle and an experimental result of a steel beam in symmetric three-point bending are reported. In this method, the measurement area of a target is attached with an adhesive tape of a known pitch grating firstly. An ordinary CCD camera is installed on a fixed point to record the image during deformation. The captured image is analyzed by performing easy image processing, i.e., thinning-out and linear interpolation, to obtain the multiple phase-shifted moiré patterns. Then, the phase distribution of the moiré pattern can be calculated using phase-shifting method. Finally, the deformation distribution is calculated by the grating pitch times the phase difference of before deformation and after deformation. The experimental results in symmetric three-point bending test show that the displacement of the steel beam at loading point agree well with those obtained by an accurate displacement sensor. The average error of displacement measurement is less than 4 μm when 2 mm grating pitch is used, and it corresponds to 1/500 of the grating pitch accuracy. This indicates that noncontact deformation distribution measurement is possible by simple and easy procedure with high accuracy, high speed, and low cost for the structural evaluation of infrastructures.     

Regularizing Effect and Local Existence for the Non-Cutoff Boltzmann Equation

The Boltzmann equation without Grad’s angular cutoff assumption is believed to have a regularizing effect on the solutions because of the non-integrable angular singularity of the cross-section. However, even though this has been justified satisfactorily for the spatially homogeneous Boltzmann equation, it is still basically unsolved for the spatially inhomogeneous Boltzmann equation. In this paper, by sharpening the coercivity and upper bound estimates for the collision operator, establishing the hypo-ellipticity of the Boltzmann operator based on a generalized version of the uncertainty principle, and analyzing the commutators between the collision operator and some weighted pseudo-differential operators, we prove the regularizing effect in all (time, space and velocity) variables on the solutions when some mild regularity is imposed on these solutions. For completeness, we also show that when the initial data has this mild regularity and a Maxwellian type decay in the velocity variable, there exists a unique local solution with the same regularity, so that this solution acquires the C ^∞ regularity for any positive time.     

Radical cyclopolymerization of dimethacrylates bearing rigid adamantane-like core derived from naturally occurring myo-inositol

Dimethacrylates with rigid adamantane-like cores were synthesized from myo-inositol orthoester via a sequence of (a) acylation or silylation of the equatorially oriented hydroxyl group, followed by (b) attachment of methacrylate groups on the axially oriented hydroxyl groups. The radical homopolymerization of these compounds proceeded via cyclopolymerization without crosslinking, as the two axially oriented methacrylate groups were fixed in close proximity with each other. The dimethacrylates underwent radical copolymerization with methyl methacrylate (MMA) to afford the corresponding polymethacrylates, exhibiting high glass transition temperatures (T_g), due to the introduction of the rigid orthoester moieties originating from the monomers and the macrocyclic structures formed via intramolecular cyclization of the two methacrylate groups of the monomers. The polymers obtained by polymerization of the dimethacrylate bearing a silylated hydroxyl group served as precursors of hydroxyl-bearing polymers, which also exhibited high T_g due to the formation of a hydrogen bonding network between the hydroxyl groups.     

Mössbauer study of paramagnetic-like behavior below the Néel temperature in a random mixture Fe x Mn1−x TiO3 withx<0.3

As a part of studies of the microscopic behavior of spins in a mixed compound with competing exchange interactions Fe _x Mn_1–x TiO₃, the Mössbauer technique has been applied to the samples withx=0.05, 0.10 and 0.20 which establish the antiferromagnetic long-range order at the respectiveT _N's and do not show reentrant transitions at lower temperatures. We have found that in each of the three samples, the paramagnetic doublet superimposes on the magnetically split spectrum belowT _N. The peak intensity of the paramagnetic doublet decreases with decreasing temperature and the paramagnetic doublet becomes undetected as sharp peaks at a temperature aroundT _N/2. However, the spectra observed at temperatures lower thanT _N/2 suggest that the paramagnetic doublet still exists, though it is highly broadened. This is interpreted as that short-range clusters of spins fluctuating rather slowly with time coexist with the spins forming the antiferromagnetic long-range order. We consider that these short-range clusters are responsible for the existence of the paramagnetic component contributing to the magnetization versus temperature curve.     

Coherent convergent beam electron diffraction for analysis of lattice fitting in PbTe/MgO bi-crystals

Coherent convergent beam electron diffraction is for the first time applied to the analysis of lattice fitting between vacuum-deposited PbTe and MgO thin crystals in the plan-view mode. The possibility of determination of the rigid-body shift is discussed on the basis of simulated diffraction patterns from the bi-crystals as well as the preliminary experimental results obtained by a 200 kV transmission electron microscope with a field emission electron gun. In the analysis, the importance of the position of interference fringes at overlaps of PbTe 200 and MgO 200 diffraction disks and that of the corresponding mirror symmetry in the whole pattern are emphasized in order to determine the rigid-body shift and the probe-position.