The role of radicals and clusters in thermal plasma flash evaporation processing

The prominent features of plasma flash evaporation may be caused by cluster deposition under high net flux of radicals. In order to clarify such features quantitatively, the atomic oxygen flux (Γ _o ) and cluster size (d) in 200 Torr RF thermal Ar-O₂ plasma were measured on the substrate. It was found that Γ _o higher than 10¹⁹ atoms/cm²·s can be easily acheived in this processing and this value corresponds to frozen atomic oxygen fraction 7 %. The cluster size of YBCO was estimated to be about 0.3 to 10 nm. 0.8 nm cluster deposition under Γ _o higher than 6 × 10¹⁸ atoms/cm²·s made it possible to deposit fine epitaxial YBCO films with Tc = 90K on SrTiO₃ (100) with extremely high deposition rate around 2.2 μm/min.     

Mössbauer spectroscopic evidence on the heme binding to the proximal histidine in unfolded carbonmonoxy myoglobin by guanidine hydrochloride

The unfolded heme structure in myoglobin is controversial because of no chance of direct X-ray structure analyses. The unfolding of carbonmonoxy myoglobin (MbCO) by guanidine hydrochloride (GdnHCl) was studied by the Mössbauer spectroscopy. The spectra show the presence of a sort of spectrum in the unfolded MbCO, independent on the concentration of GdnHCl from 1 to 6 M and the increase of the fraction of unfolded MbCO, depending on the GdnHCl concentration. The isomer shift of the iron of heme in the unfolded MbCO was identified to be different from that of the native MbCO as the globin structure in Mb collapses under the unfolded conditions. This result and the existing related Mössbauer data proved that the heme in the unfolded MbCO may remain coordinated to the proximal histidine.     

Simultaneous measurements of reactive scalar and velocity in a planar liquid jet with a second-order chemical reaction

This paper presents a new experimental approach for simultaneous measurements of velocity and concentration in a turbulent liquid flow with a chemical reaction. For the simultaneous measurements, we developed a combined probe consisting of an I-type hot-film probe and an optical fiber probe based on the light absorption spectrometric method. In a turbulent planar liquid jet with a second-order chemical reaction $(\mathrm{A}+\mathrm{B}\rightarrow \mathrm{R})$ , streamwise velocity and concentrations of all reactive species are measured by the combined probe. The turbulent mass fluxes of the reactive species are estimated from the simultaneous measurements. The results show that the influence of the chemical reaction on the turbulent mass flux of the reactant species near the jet exit is different from its influence in other regions, and the turbulent mass flux of the product species has a negative value near the jet exit and a positive value in other regions.     

Precision measurement of neutrino oscillation parameters with KamLAND

The KamLAND experiment has determined a precise value for the neutrino oscillation parameter Deltam21(2) and stringent constraints on theta12. The exposure to nuclear reactor antineutrinos is increased almost fourfold over previous results to 2.44 x 10(32) proton yr due to longer livetime and an enlarged fiducial volume. An undistorted reactor nu[over]e energy spectrum is now rejected at >5sigma. Analysis of the reactor spectrum above the inverse beta decay energy threshold, and including geoneutrinos, gives a best fit at Deltam21(2)=7.58(-0.13)(+0.14)(stat) -0.15+0.15(syst) x 10(-5) eV2 and tan2theta12=0.56(-0.07)+0.10(stat) -0.06+0.10(syst). Local Deltachi2 minima at higher and lower Deltam21(2) are disfavored at >4sigma. Combining with solar neutrino data, we obtain Deltam21(2)=7.59(-0.21)+0.21 x 10(-5) eV2 and tan2theta12=0.47(-0.05)+0.06.     

Gold(I)‐Catalyzed Cascade Cyclization Reactions of Allenynes for the Synthesis of Fused Cyclopropanes and Acenaphthenes

A gold‐catalyzed reaction of phenylene‐tethered allenynes with benzofurans gave 1‐(naphth‐1‐yl)cyclopropa[b]benzofuran derivatives, whereas the reaction of 1‐allenyl‐2‐ethynyl‐3‐methylbenzene derivatives in the absence of benzofurans gave acenaphthenes in good yields. These results can be rationalized by nucleophilic attack of the alkyne moiety on an activated allene to form a vinyl cation intermediate.     

Energy‐resolved mass spectrometry for differentiation of the fluorine substitution position on the phenyl ring of fluoromethcathinones

A reliable method for structural analysis is crucial for the forensic investigation of new psychoactive substances (NPSs). Towards this end, mass spectrometry is one of the most efficient and facile methods for the identification of NPSs. However, the differentiation among 2‐, 3‐, and 4‐fluoromethcathinones (o‐, m‐, and p‐FMCs), which are ring‐fluorinated positional isomers part of the major class of NPSs referred to as synthetic cathinones, remains a challenge. This is mostly due to their similar retention properties and nearly identical full scan mass spectra, which hinder their identification. In this study, we describe a novel and practical method for differentiating the fluorine substitution position on the phenyl ring of FMCs, based on energy‐resolved mass spectrometry (ERMS) using an electron ionization‐triple quadrupole mass spectrometer. ERMS measurements showed that the three FMC positional isomers exhibited differences in relative abundances of both the fluorophenyl cation (m/z 95) and the fluorobenzoyl cation (m/z 123). The logarithmic plots of the abundance ratio of these two cations (m/z 95 to m/z 123) as a function of the collision energy (CE) followed the order of o‐FMC < p‐FMC < m‐FMC at each CE, which allowed the three isomers to be unambiguously and reliably differentiated. The theoretical dissociation energy calculations confirmed the relationship obtained by ERMS analyses, and additional ERMS measurements of methylmethcathinone positional isomers showed that the differences in abundance among the FMCs were attributed to the differences in their collision‐induced dissociation reactivities arising from the halogen‐induced resonance effects on the phenyl ring. Moreover, the method for differentiation described herein was successfully applied to the actual samples containing seized drugs. We expect that the described methodology will also contribute significantly to the reliable and accurate structural identification of NPSs in the fields of therapeutic, clinical, and forensic toxicology.     

Anthracene‐Attached Persistent Tricyclic Aromatic Hydrocarbon Radicals

Anthracene‐attached tricyclic aromatic hydrocarbon radicals having different central polygons, Ant‐5 , Ant‐6 , and Ant‐7 , were synthesized to evaluate the role of an anthracene substituent group in the stability and reactivity of tricyclic aromatic hydrocarbon radicals. The bulky anthryl group effectively protects a carbon atom with high spin density, resulting in high persistence of the radicals. On the other hand, the combination of the anthryl group and the tricyclic aromatic scaffold makes the molecular structure drastically change from a twisted form to a folded form and an unpaired electron moves into the anthryl moiety, eventually affording a tail‐to‐tail σ‐dimer.     

The design and characteristic features of a new time-of-flight mass spectrometer with a spiral ion trajectory

A new time-of-flight (TOF) mass spectrometer with a corkscrew ion trajectory was designed and constructed. The spiral trajectory was realized by using four toroidal electrostatic sectors. Each had fifteen-stories made of sixteen Matsuda plates piled up inside a cylindrical electrostatic sector. The ions passed the four toroidal electrostatic sectors sequentially and revolved along a figure-eight-shaped orbit on a certain projection plane. During the multiple revolutions, each ion trajectory was shifted by 50 mm per cycle on a direction perpendicular to the projection plane, thus generating a spiral trajectory. The flight path length of one cycle was 1.308 m so that the maximum flight path length became approximately 20 m. The mass resolution, mass accuracy, and ion transmission were tested by utilizing an orthogonally coupled electron ionization source. A mass resolution of 35,000 (FWHM) for m/z greater than 300 was achieved. Even in a lower mass region, mass resolutions of more than 20,000 (FWHM) were confirmed with a doublet of (12)C(5)(1)H(5)(14)N(+) and (13)C(12)C(5)(1)H(6)(+). The mass accuracy was also improved such that it was better than 1 ppm with only one internal standard peak. An ion transmission of approximately of 100% was observed for 15 cycles.