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61.
Reinmöller M Ulbrich A Ikari T Preiss J Höfft O Endres F Krischok S Beenken WJ 《Physical chemistry chemical physics : PCCP》2011,13(43):19526-19533
We have recently measured core level and valence band XPS, UPS, and MIES spectra of two room temperature ionic liquids composed of bis(trifluoromethylsulfonyl)imide anions ([Tf(2)N](-)) and either 1-ethyl-3-methyl-imidazolium ([EMIm](+)) or 1-octyl-3-methyl-imidazolium cations ([OMIm](+)). [T. Ikari, A. Keppler, M. Reinm?ller, W. J. D. Beenken, S. Krischok, M. Marschewski, W. Maus-Friedrichs, O. H?fft and F. Endres, e-J. Surf. Sci. Nanotechnol., 2010, 8, 241.] In the present work we analyze these spectra by means of partial density of states (pDOS) as calculated from a single ion pair of the respective ionic liquid using density functional theory (DFT). Subsequently we reconstruct the XPS and UPS spectra by considering photoemission cross sections and analyze the MIES spectra by pDOS, which provides us decisive hints to the ionic liquid surface structure. 相似文献
62.
Kosumi D Kusumoto T Fujii R Sugisaki M Iinuma Y Oka N Takaesu Y Taira T Iha M Frank HA Hashimoto H 《Physical chemistry chemical physics : PCCP》2011,13(22):10762-10770
Carotenoids containing a carbonyl group in conjugation with their polyene backbone are naturally-occurring pigments in marine organisms and are essential to the photosynthetic light-harvesting function in aquatic algae. These carotenoids exhibit spectral characteristics attributed to an intramolecular charge transfer (ICT) state that arise in polar solvents due to the presence of the carbonyl group. Here, we report the spectroscopic properties of the carbonyl carotenoid fucoxanthin in polar (methanol) and nonpolar (cyclohexane) solvents studied by steady-state absorption and femtosecond pump-probe measurements. Transient absorption associated with the optically forbidden S(1) (2(1)A) state and/or the ICT state were observed following one-photon excitation to the optically allowed S(2) (1(1)B) state in methanol. The transient absorption measurements carried out in methanol showed that the ratio of the ICT-to-S(1) state formation increased with decreasing excitation energy. We also showed that the ICT character was clearly visible in the steady-state absorption in methanol based on a Franck-Condon analysis. The results suggest that two spectroscopic forms of fucoxanthin, blue and red, exist in the polar environment. 相似文献
63.
Chikara Shito Keitaro Okamoto Yuki Sato Ryuji Watanabe Tomonori Ohashi Kazuhiro Fuchizaki 《高压研究》2013,33(3):499-508
ABSTRACTHigh pressure hydrous phases with distorted rutile-type structure have attracted much interest as potential water reservoirs in the Earth’s mantle. An in-situ X-ray diffraction study of β-CrOOH was performed at high pressures of up to 6.2?GPa and high-temperatures of up to 700?K in order to clarify the temperature effect on compression behaviors of β-CrOOH. The P-V-T data fitted to a Birch–Murnaghan equation of state yielded the following results: isothermal bulk modulus KT0?=?191(4)?GPa, temperature derivative (?KT/?T)P?=??0.04(2)?GPa?K?1, and volumetric thermal expansion coefficient α?=?3.3(2)?×?10?5?K?1. In this study, at 300?K, the a-axis became less compressible at pressures above 1–2?GPa. We found that the pressure where the slopes of a/b and a/c ratios turned positive increased with temperature. This is the first experimental study indicating the temperature dependence of the change in the axial compressibility in distorted rutile-type M3+OOH. 相似文献
64.
We have succeeded in the total synthesis of siomycin A, a representative compound of the thiostrepton family of peptide antibiotics, featuring the one-pot cyclization-elongation of our strategic intermediates and the late-stage formations of the thiazoline and dehydroamino acid moieties. 相似文献
65.
Yasuyuki Tsuboi Kensaku Okada Shoji Ishizaka Noboru Kitamura 《Analytical sciences》2005,21(3):303-308
We found that alpha-diketones (2,3-butanedione (BD) and 1-phenyl-1,2-propanedione (PPD)) were very suitable luminescence probes for studying the properties of a perfluorinated solvent (i.e., fluorous solvent; perfluoromethylcyclohexane (PFMC)), since these compounds were soluble in PFMC and showed long-lived phosphorescence even at room temperature. The phosphorescence lifetime (tau(p)) of BD in PFMC (650 micros) was much longer than that in cyclohexane (CH, 270 micros). The longer tau(p) value of BD in PFMC was ascribed to the variation of the intersystem crossing rate constant (k(isc)) from the excited triplet state (T1) to the ground state (S0) with the solvent. Some possible reasons for the change in k(isc) were discussed in terms of solute-solvent interactions. Furthermore, by utilizing phosphorescence quenching of BD by pyrene, we, determined a rate constant of the diffusion-controlled reaction in PFMC. Characteristic behaviors of mixing/separation processes between PFMC and a common organic solvent observed by Schlieren photographs were also reported. 相似文献
66.
Synthesis of the dihydroquinoline portion of thiostrepton, the siomycins, and the thiopeptins, members of the thiostrepton family of peptide antibiotics, has been achieved featuring the one-pot olefination via the Matsumura-Boekelheide rearrangement “using trifluoromethanesulfonic anhydride and triethylamine” and the stereoselective addition reaction controlled by the stereocenter of the peri-position. 相似文献
67.
Yoshiaki Hamada Kazuko Hashiguchi Masamichi Tsuboi Yoshinori Koga Shigeo Kondo 《Journal of Molecular Spectroscopy》1984,105(1):70-80
Methyleneimine was detected in the gas phase by a moderately high resolution infrared spectrometer as one of the intermediate species produced by a pyrolysis of amines. Observed vibrational frequencies of some isotopic derivatives have been combined with the ab initio values to reach a most reliable force constants set. Some other spectroscopic parameters, involving geometrical parameters and dipole moment derivatives, have also been calculated ab initio and compared with the observation. Its half-life in our experimental apparatus was about 10 min, which is much longer than the previously reported values, 0.1 or 10 sec. 相似文献
68.
69.
70.
Yoshiaki Amatatsu Yoshiaki Hamada Masamichi Tsuboi Masaaki Sugie 《Journal of Molecular Spectroscopy》1985,111(1):29-41
The infrared spectrum of N-methylvinylamine was observed for the first time in the gas phase by the pyrolysis of propyleneimine. The half-life of this molecule was about 40 sec under our experimental conditions, and the molecule isomerized immediately into its tautomer, N-methylethylideneimine. The absorption bands were assigned by the help of an ab initio MO calculation. 相似文献