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61.
A confocal micro‐X‐ray fluorescence (micro‐XRF) instrument equipped with a vacuum chamber was newly developed. The instrument is operated under a vacuum condition to reduce the absorption of XRF in the atmosphere. Thin metal layers were developed to evaluate the confocal volume, corresponding to depth resolution. A set of thin metal layers (Al, Ti, Cr, Fe, Ni, Cu, Zr, Mo, and Au) was prepared by a magnetron sputtering technique. The depth resolutions of the new instrument were varied from 56.0 to 10.9 µm for an energy range from 1.4 to 17.4 keV, respectively. The lower limit of detection (LLD) was estimated by comparison with a glass standard reference material NIST SRM 621). The LLDs obtained by a conventional micro‐XRF were compared with the LLDs obtained by a confocal micro‐XRF instrument. The LLDs were improved in the measurement under confocal configuration because of the reduction of background intensity. Finally, layered materials related to forensic investigation were measured. The confocal micro‐XRF instrument was able to nondestructively obtain the distribution of light elements that cannot be detected by measurement in air. Copyright © 2013 John Wiley & Sons, Ltd. 相似文献
62.
Kozo Okazaki Masato Hibi Yoshitaka Teraoka Takuya Nakata Kouichi Yonetani Shunji Sugai 《Journal of Physics and Chemistry of Solids》2008,69(12):3078-3081
We have investigated electron-boson coupling in the optical conductivity of high-Tc superconductors through the optical self-energy. The real part of the self-energy (ReΣop(ω)) of YBa2Cu3Oy (YBCO) shows a characteristic doping dependence. In the optimally doped YBCO, ReΣop(ω) has a single peak around 65 meV, which corresponds to the kink structure of the band dispersion. On the other hand, in the under-doped YBCO, the peak structure of ReΣop(ω) splits into two parts. To evaluate contribution from the phonons in electron-boson coupling, we have measured oxygen-isotope effects by substituting 16O→18O for the optimally doped and under-doped YBCO. 相似文献
63.
Copper-catalyzed reactions of carbonyl-ene-nitriles with carbon nucleophiles, such as aromatics and ketones, afforded pyrrolin-2-ones (gamma-lactam) in excellent yield. The reaction mechanism involves addition reactions with a ketimine moiety of the 2-aza-2,4-cyclopentadienone intermediate, which is formed via hydration of a nitrile moiety followed by dehydrative cyclization. 相似文献
64.
We have applied recently two XRF (micro x‐ray fluorescence) methods [micro‐Grazing Exit XRF (GE‐XRF) and confocal 3D‐XRF] to Japanese lacquerware ‘Tamamushi‐nuri.’ A laboratory grazing‐exit XRF (GE‐XRF) instrument was developed in combination with a micro‐XRF setup. A micro x‐ray beam was produced by a single capillary and a pinhole aperture. Elemental x‐ray images (2D images) obtained at different analyzing depths by micro GE‐XRF have been reported. However, it was difficult to directly obtain depth‐selective x‐ray spectra and 2D images. A 3D XRF instrument using two independent polycapillary x‐ray lenses and two x‐ray sources (Cr and Mo targets) was also applied to the same sample. 2D XRF images of a Japanese lacquerware showed specific distributions of elements at the different depths, indicating that ‘Tamamushi‐nuri’ lacquerware has a layered structure. The merits and disadvantages of both the micro GE‐XRF and confocal micro XRF methods are discussed. Copyright © 2009 John Wiley & Sons, Ltd. 相似文献
65.
Thioacetals were found to be effective precursors to generate and accumulate alkoxycarbenium ions based on direct and indirect cation pool methods. Alkoxycarbenium ions thus generated reacted with carbon nucleophiles such as allylsilanes and enol silyl ethers to give C-C bond formation products in good yields. 相似文献
66.
Ohe K Fujita M Matsumoto H Tai Y Miki K 《Journal of the American Chemical Society》2006,128(29):9270-9271
The ruthenium-catalyzed isomerization of diynes and triynes involving propargyl carboxylate moieties affords dienynes and dienediynes, respectively. The [1,n]-metallotropic shift (n = 3, 5) (carbene walk) of in situ generated alkynyl carbene complexes has been proposed for the catalytic isomerization reaction. 相似文献
67.
Suga S Matsumoto K Ueoka K Yoshida J 《Journal of the American Chemical Society》2006,128(24):7710-7711
A sequential one-pot indirect cation pool method has been developed. The method involves the electrochemical generation and accumulation of ArS(ArSSAr)+ at low temperature (step 1) and the follow-up reaction with a thioacetal to generate an alkoxycarbenium ion pool (step 2), which reacts with various carbon nucleophiles (step 3). Steps 2 and 3 are extremely fast. The electrogenerated ArS(ArSSAr)+ was well-characterized by 1H NMR and CSI-MS. The alkoxycarbenium ion pool generated by the present indirect method exhibited 1H and 13C NMR spectra and thermal stability similar to those of the alkoxycarbenium ion pool generated by the direct electrochemical method. 相似文献
68.
Rajca A Boratyński PJ Olankitwanit A Shiraishi K Pink M Rajca S 《The Journal of organic chemistry》2012,77(5):2107-2120
We describe the synthesis and electronic properties of ladder oligomers of poly(m-aniline) that may be considered as derivatives of azaacenes with cross-conjugated π-systems. Syntheses of ladder oligo(m-aniline)s with 9 and 13 collinearly fused six-membered rings employed Pd-catalyzed aminations and Friedel-Crafts-based ring closures. Structures were 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. All compounds have planar "azaacene" moieties. The experimental band gaps E(g) ≈ 3.5-3.65 eV, determined by the UV-vis absorption onsets, were in agreement with the TD-DFT-computed vertical excitation energies to the S(1) state. Fluorescence quantum yields of up to 20% were found. Electrochemically estimated HOMO energies of -4.8 eV suggested propensity for a facile one-electron oxidation and just sufficient environmental stability toward oxygen (O(2)). For two oligomers with "tetraazanonacene" moieties, potentials of E(4+/3+) ≈ 1.6-1.7 V vs SCE were determined for four-electron oxidation to the corresponding tetraradical tetracations. 相似文献
69.
Kouichi Tsuji Zoya Spolnik Kazuaki Wagatsuma Rik Nullens RenéE. Van Grieken 《Mikrochimica acta》2000,132(2-4):357-360
In conventional electron probe microanalysis (EPMA), the electron-induced X-rays are measured at large take-off angles of
about 45°. In the grazing exit EPMA (GE-EPMA) method, they are measured at small angles (< 1°). X-rays emitted from deep positions
can not be detected at grazing exit angles due to refraction effects at sample-vacuum interface; therefore, it is possible
to measure X-rays emitted only from near the surface with a low background. GE-EPMA is especially suitable for the analysis
of particles deposited on a flat sample carrier. The detection limits of GE-EPMA were investigated for artificial particles
(Al2O3, Fe2O3 and PbO2 , particle sizes: 1 ∼ 18 μm) deposited on flat sample carriers of Au thin films–Si wafers. The detection limits improved
with decreasing exit angle. The detection limits for characteristic X-rays at an exit angle of approximately 1.1° were 2–4
times lower than at 45°. A minimum detection limit of ca. 0.1% was obtained for Al in small particles. 相似文献
70.