Mass balance method for purity assay of phthalic acid esters: development of primary reference materials as traceability sources in the Japan Calibration Service System

Purity assay of high-purity materials (HPMs) of phthalic acid esters (PAEs) was carried out by means of a mass balance method. In this method, chromatographic methods such as gas chromatography-flame ionization detector (GC-FID) and/or high-performance liquid chromatography (HPLC) in combination with other methods such as Karl-Fischer (KF) titration and vacuum evaporation (VE) were applied. The sum of the impurities estimated by these methods allowed the estimation of the purity of the main component by difference. Seven PAEs with varying side chain structures and levels of impurities were analysed on a systematic way in which impurities were classified into several groups in terms of their abundance, availability of qualitative information and availability of authentic compounds, etc. The absolute quantity of each impurity was determined by GC-FID and/or HPLC based on the calibration made by the authentic compounds of impurities whenever available. The purities in mass fraction of these PAEs were certified at the National Metrology Institute of Japan (NMIJ), and the PAEs were registered as primary reference materials playing an essential role in linking the metrological traceability of the Japan Calibration Service System (JCSS) to the International System of Units (SI).     

Activity of SiDbCl in the Electrooxidation of Ascorbic Acid,Dopamine, and Uric Acid

Selective electroanalytical responses for ascorbic acid, dopamine and uric acid at a carbon modified electrode based on 3‐n‐propyl‐1‐azonia‐4‐azabicyclo[2.2.2]octane silsesquioxane chloride (SiDbCl) is reported. The overlapped peaks observed at an unmodified electrode are resolved into three well defined voltammetric peaks allowing the simultaneous determination of the three species. Detection limits of 37, 0.3 and 0.1 μmo L⁻¹ of ascorbic acid, dopamine and uric acid, respectively, were calculated from calibration curves based on differential pulse voltammetric experiments performed in Britton ‐ Robinson buffer solution at pH 7.04.     

3]Rotaxane-based dinuclear palladium catalysts for ring-closure Mizoroki-Heck reaction

[3]Rotaxane containing two Pd centers in the cyclic compounds catalyzes a Mizoroki-Heck reaction of substrates with two iodophenyl groups with bisacrylate. Formation of the cyclic products is enhanced by the rotaxane catalyst more smoothly than Pd(OAc)(2).     

Structural study of a series of layered rare-earth hydroxide sulfates

We report structure analysis of a new family of rare-earth hydroxides Ln(2)(OH)(4)SO(4)·2H(2)O (Ln = Pr, Nd, Sm, Eu, Gd, Tb) from synchrotron X-ray and electron diffraction data. Rietveld profile analysis revealed that all members were isostructural and crystallized in a face-centered monoclinic system A2/m (No. 12), in which the monoclinic angles were approximately equal to the right angle, varying from 90.387(1)° for Pr sample to 90.0718(3)° for Tb sample. The structure consisted of LnO(9) polyhedra connected by μ(3)-hydroxyl groups and μ(2)-water molecules, forming a corrugated two-dimensional layer, which was pillared by bidentated sulfate ions. This series of compounds had a supercell a' = 2a, b' = 2b because of the local orientation ordering of SO(4)(2-). Structural features along the series, such as unit-cell parameters and average Ln-O distances, represented a progressive contraction associated with the shrinking radius of the lanthanide cations from Pr to Tb.     

Characterization of a synthetic peroxodiiron(III) protein model complex by nuclear resonance vibrational spectroscopy

The vibrational spectrum of an η(1),η(1)-1,2-peroxodiiron(III) complex was measured by nuclear resonance vibrational spectroscopy and fit using an empirical force field analysis. Isotopic (18)O(2) labelling studies revealed a feature involving motion of the {Fe(2)(O(2))}(4+) core that was not previously observed by resonance Raman spectroscopy.     

Formation and dielectric properties of anodic oxide films on Zr–Al alloys

Zr–Al alloys containing up to 26 at.% aluminum, prepared by magnetron sputtering, have been anodized in 0.1 mol dm⁻³ ammonium pentaborate electrolyte, and the structure and dielectric properties of the resultant anodic oxide films have been examined by grazing incidence X-ray diffraction, transmission electron microscopy, Rutherford backscattering spectroscopy, and AC impedance spectroscopy. The anodic oxide film formed on zirconium consists of monoclinic and tetragonal ZrO₂ with the former being a major phase. Two-layered anodic oxide films, comprising an outer thin amorphous layer and an inner main layer of crystalline tetragonal ZrO₂ phase, are formed on the Zr–Al alloys containing 5 to 16 at.% aluminum. Further increase in the aluminum content to 26 at.% results in the formation of amorphous oxide layer throughout the thickness. The anodic oxide films become thin with increasing aluminum content, while the relative permittivity of anodic oxide shows a maximum at the aluminum content of 11 at.%. Due to major contribution of permittivity enhancement, the maximum capacitance of the anodic oxide films is obtained on the Zr–11 at.% Al alloy, being 1.7 times than on zirconium at the formation voltage of 100 V.     

Nitrosylation of Nitric‐Oxide‐Sensing Regulatory Proteins Containing [4Fe‐4S] Clusters Gives Rise to Multiple Iron–Nitrosyl Complexes

The reaction of protein‐bound iron–sulfur (Fe‐S) clusters with nitric oxide (NO) plays key roles in NO‐mediated toxicity and signaling. Elucidation of the mechanism of the reaction of NO with DNA regulatory proteins that contain Fe‐S clusters has been hampered by a lack of information about the nature of the iron‐nitrosyl products formed. Herein, we report nuclear resonance vibrational spectroscopy (NRVS) and density functional theory (DFT) calculations that identify NO reaction products in WhiD and NsrR, regulatory proteins that use a [4Fe‐4S] cluster to sense NO. This work reveals that nitrosylation yields multiple products structurally related to Roussin's Red Ester (RRE, [Fe₂(NO)₄(Cys)₂]) and Roussin's Black Salt (RBS, [Fe₄(NO)₇S₃]. In the latter case, the absence of ³²S/³⁴S shifts in the Fe?S region of the NRVS spectra suggest that a new species, Roussin's Black Ester (RBE), may be formed, in which one or more of the sulfide ligands is replaced by Cys thiolates.     

All-Fiber Optical Add-Drop Multiplexer Using a Pair of Fiber Grating Couplers

A new all-fiber optical add-drop multiplexer (ADM) using a pair of fiber grating couplers (FGCs) was proposed and first demonstrated. It was theoretically and experimentally shown that both drop and add efficiencies could be maximized in the proposed ADM. It was also clarified that the crosstalk between dropped and added signals could be improved in the proposed ADM compared with that in the single FGC. Drop and add operations in the ADM for 3-channel WDM signals with 1.6 nm wavelength spacing were confirmed. The ADM with signal amplification ability, which consists of a pair of FGCs, an EDF, and a pump-LD, was proposed and demonstrated. It was confirmed that the dropped and transmitted optical signals could be amplified in the ADM, and would be able to expand fiber routing spans.