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91.
Lu X Nakajima K Iiduka Y Nikawa H Mizorogi N Slanina Z Tsuchiya T Nagase S Akasaka T 《Journal of the American Chemical Society》2011,133(48):19553-19558
A Sc(2)C(84) isomer, previously assumed to be Sc(2)@C(84), is unambiguously identified as a new carbide cluster metallofullerene Sc(2)C(2)@C(s)(6)-C(82) using both NMR spectroscopy and X-ray crystallography. The (13)C-nuclei signal of the internal C(2)-unit was observed at 244.4 ppm with a 15% (13)C-enriched sample. Temperature-dependent dynamic motion of the internal Sc(2)C(2) cluster is also revealed with NMR spectrometry. Moreover, the chemical property of Sc(2)C(2)@C(s)(6)-C(82) is investigated for the first time using 3-triphenylmethyl-5-oxazolidinone (1) which provides a 1,3-dipolar reagent under heating. Regarding the low cage symmetry of this endohedral which contains 44 types of nonequivalent cage carbons, it is surprising to find that only one monoadduct isomer is formed in the reaction. Single-crystal X-ray results of the isolated pyrrolidino derivative Sc(2)C(2)@C(s)(6)-C(82)N(CH(2))(2)Trt (2) reveal that the addition takes place at a [6,6]-bond junction, which is far from either of the two Sc atoms. Such a highly regioselective addition pattern can be reasonably interpreted by analyzing the frontier molecular orbitals of the endohedral. Electronic and electrochemical investigations reveal that adduct 2 has a larger highest occupied molecular orbital-lowest unoccupied molecular orbital (HOMO-LUMO) gap than pristine Sc(2)C(2)@C(s)(6)-C(82); accordingly, it is more stable. 相似文献
92.
Theoretical studies of the ground and lowest excited singlet and triplet states of a series of titanium dioxide ring structures, (TiO(2))(2n), n = 3-9, are reported. Calculations are based on many-electron configuration theory, where energies of states and geometrical structures are determined by variational energy minimization. The lowest energy excited states correspond to excitations from oxygen 2p levels to unoccupied 3d orbitals on titanium. For each ring system, two types of excited state solutions are investigated: those that maintain periodic symmetry for individual orbitals and solutions that allow the symmetry to be broken. The latter solutions which correspond to localized states or excitons are found to be significantly lower in energy than the symmetric solutions. We compare the vertical excitation energy of these well-defined geometrical structures with size effects reported in experimental studies. 相似文献
93.
Kamisaki-Horikoshi N Okada Y Takeshita K Sameshima T Kawasaki S Kawamoto S Fratamico PM 《Journal of AOAC International》2011,94(3):857-862
The Bacteriological Analytical Manual (BAM) Salmonella pre-enrichment broth [lactose (LAC) broth], buffered peptone water, and universal pre-enrichment (UP) broth were compared with TA10 broth, developed in our laboratory, for recovery of heat- and freeze-injured Salmonella (55 degrees C for 2-20 min and -20 degrees C for 2 months, respectively) from beef. Beef samples were contaminated with single Salmonella serovars, and contamination levels of 0.44 to <0.001 most probable number (MPN)/g and 0.74 to 0.14 MPN/g were used for heat- and freezing-induced injury studies, respectively. Twenty test portions (25 g) of the contaminated beef were pre-enriched in each broth, and the BAM Salmonella culture method was used thereafter. There was a significant difference (chi2 = 7.73) in recovery of heat-injured Salmonella between TA10 broth and LAC broth, 189 (67.5%) versus 156 (55.7%) positive samples, respectively, determined by plating onto selective agars and identification by biochemical tests. For the recovery of freeze-injured Salmonella, there was a significant difference (chi2 = 24.7) between TA10 and LAC broth, 189 (72.7%) versus 133 (51.2%) positive samples, respectively. TA10 broth was more effective than LAC broth and UP broth for recovery of freeze-injured Salmonella. The results indicate that TA10 broth should be used instead of LAC broth for testing of beef that may be contaminated with heat- and freeze-injured Salmonella spp. 相似文献
94.
Zaima N Goto-Inoue N Hayasaka T Enomoto H Setou M 《Analytical and bioanalytical chemistry》2011,400(7):1865-1871
It has become necessary to assess the authenticity of beef origin because of concerns regarding human health hazards. In this
study, we used a metabolomic approach involving matrix-assisted laser desorption/ionization imaging mass spectrometry to assess
the authenticity of beef origin. Highly accurate data were obtained for samples of extracted lipids from beef of different
origin; the samples were grouped according to their origin. The analysis of extracted lipids in this study ended within 10 min,
suggesting this approach can be used as a simple authenticity assessment before a definitive identification by isotope analysis. 相似文献
95.
Matsumoto J Sugiura Y Yuki D Hayasaka T Goto-Inoue N Zaima N Kunii Y Wada A Yang Q Nishiura K Akatsu H Hori A Hashizume Y Yamamoto T Ikemoto K Setou M Niwa S 《Analytical and bioanalytical chemistry》2011,400(7):1933-1943
Schizophrenia is one of the major psychiatric disorders, and lipids have focused on the important roles in this disorder. In fact, lipids related to various functions in the brain. Previous studies have indicated that phospholipids, particularly ones containing polyunsaturated fatty acyl residues, are deficient in postmortem brains from patients with schizophrenia. However, due to the difficulties in handling human postmortem brains, particularly the large size and complex structures of the human brain, there is little agreement regarding the qualitative and quantitative abnormalities of phospholipids in brains from patients with schizophrenia, particularly if corresponding brain regions are not used. In this study, to overcome these problems, we employed matrix-assisted laser desorption/ionization imaging mass spectrometry (IMS), enabling direct microregion analysis of phospholipids in the postmortem brain of a patient with schizophrenia via brain sections prepared on glass slides. With integration of traditional histochemical examination, we could analyze regions of interest in the brain at the micrometric level. We found abnormal phospholipid distributions within internal brain structures, namely, the frontal cortex and occipital cortex. IMS revealed abnormal distributions of phosphatidylcholine molecular species particularly in the cortical layer of frontal cortex region. In addition, the combined use of liquid chromatography/electrospray ionization tandem mass spectrometry strengthened the capability for identification of numerous lipid molecular species. Our results are expected to further elucidate various metabolic processes in the neural system. 相似文献
96.
Shiraki T Dawn A Le TN Tsuchiya Y Tamaru S Shinkai S 《Chemical communications (Cambridge, England)》2011,47(25):7065-7067
A thermo- and light-responsive system consisting of single-walled carbon nanotube and helical polysaccharide modified with poly(N-isopropylacrylamide) side-chains has been developed through supramolecular polymer wrapping. Coagulation of the complex can be induced by the external stimuli, which leads to a catch-and-release action of a porphyrin derivative. 相似文献
97.
Naomi Warashina Masahiro Tsuchiya Kaori Ishimaru Takakazu Kojima 《Journal of Thermal Analysis and Calorimetry》2011,105(2):473-477
Imbalance condensation of diaminophenylbenzimidazole, DAPBI, with terephthaloyl chloride, TPC was conducted for the purpose
of synthesis of macromonomers, expected to be used in syntheses of aromatic polyamides with structural regularities. The products
are soluble in dimethylsulfoxide—d6, and their 1H NMR spectra indicate that all the products are carboxyl-terminated. The
signal of carboxyphenyl linked to chain ends is different from that of terephthaloyl in the 1H NMR spectra. By use of the
ratio of the signal intensity of the former to that of the latter, the number-average degree of polymerization, DP
NMR is determined. With the mole ratio in feed, DP
NMR of the product increases. The TG thermograms of the products are a multistage one. Each stage is classified by temperature
and mass loss at an inflection point. Mass loss of each stage classified by temperature at an inflection point corresponds
to mass fraction of an aromatic amide with a characteristic degree of polymerization, DP, and that is, the DP distribution of the products is roughly estimated from the TG thermograms. The DP distribution of macromonomers influences performance of aromatic polyamides with structural regularities, derived from the
macromonomers. The convenient estimation method of DP distribution by TG is useful in industries of high-performance polymers. To the knowledge, such convenient technique has
never reported. 相似文献
98.
99.
Tsuchiya T Imai H Miyoshi S Glans PA Guo J Yamaguchi S 《Physical chemistry chemical physics : PCCP》2011,13(38):17013-17018
The electronic structure and modification of the local interatomic structure of a reactive sputtered amorphous tantalum oxide (a-TaO(x)) thin film with the variation of oxygen nonstoichiometry, x in a-TaO(x) have been investigated by X-ray absorption spectroscopy (XAS), X-ray photoemission spectroscopy (XPS), Raman scattering spectroscopy, and Rutherford back scattering spectroscopy. A parallel chemical shift of Ta4f(7/2) and O1s core levels observed with the variation of x indicates the Fermi level shift by reduction and oxidation in the framework of the rigid band model. Extended X-ray absorption fine structure (EXAFS) suggests both the increase of average coordination number of the first Ta-O shell in polyhedra and a considerable reduction of the average Ta-O bond length with the increase of x. The relative intensity of Raman shift peaks at 670 cm(-1) and 815 cm(-1), corresponding to Ta-O stretching of TaO(6) octahedra and TaO(5) probably with a pyramidal form, respectively, drastically changes between x = 2.47 to 1.86, suggesting the change in the predominant polyhedron from TaO(6) to TaO(5) with a modification in multiplicity of oxygen by the reorganization of the polyhedral network. 相似文献
100.
Kentaro Shinoda Tomohiko Nakajima Tetsuo Tsuchiya 《Applied physics. B, Lasers and optics》2013,113(3):479-484
The epitaxial and polycrystalline growth of lanthanum strontium manganite films on single crystalline strontium titanate and lanthanum aluminate substrates, respectively, under the irradiation with XeCl lasers in the excimer laser-assisted metal organic deposition (ELAMOD) process have been previously reported. In order to investigate the growth phenomena, we monitored the thermal radiation from the sample surfaces irradiated with a pulsed ultraviolet laser in situ with near-infrared sensors. The cooling of the lanthanum strontium manganite films on strontium titanate substrates was significantly slower than that of films on lanthanum aluminate substrates. A similar behavior was also observed by the numerical simulation study. This difference in the cooling decay curves may play an important role in the mode by which crystal growth occurs in the ELAMOD process. 相似文献