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121.
Takumi Kusano Kenta Fujii Masaaki Tabata Mitsuhiro Shibayama 《Journal of solution chemistry》2013,42(10):1888-1901
Aggregation structures of 1-alkyl-3-methylimidazolium based ionic liquids (ILs) in aqueous solution were investigated by small-angle neutron scattering (SANS) from the viewpoint of alkyl chain length, n, and anions (Cl?, Br? and trifluoromethanesulfonate, $ {\text{CF}}_{3} {\text{SO}}_{3}^{ - } $ ). In [C4mIm+]-based IL systems, no noticeable SANS intensity was observed for all of the systems examined here, although aqueous [C4mIm+][ $ {\text{BF}}_{4}^{ - } $ ] solutions show a significant SANS profile originating from concentration fluctuations in the solution (Almasy et al. J Phys Chem B 112:2382–2387, 2008). This suggests that [C4mIm+][Cl?], [C4mIm+][Br?] and [C4mIm+][ $ {\text{CF}}_{3} {\text{SO}}_{3}^{ - } $ ] homogeneously mix with water, unlike the [C4mIm+][ $ {\text{BF}}_{4}^{ - } $ ] system, due to preferential hydration of the ions. In the case of the C n mIm cations with longer alkyl chain lengths (n = 8 and 12), SANS profiles were clearly observed in the aqueous solutions at IL concentrations of C IL > 230 and 20.0 mmol·dm?3, respectively. For aqueous [C8mIm+][Br?] solutions, the asymptotic behavior of the scattering function varied largely from I(q) ~ q ?2 to ~q ?4 with increasing C IL, indicating that the solution changes from an inhomogeneous mixing state to a nano-scale micelle state. Aqueous [C12mIm+][Br?] solutions show a typical SANS profile for micelle formation in solution. It was found from a model-fitting analysis that the structure of the [C12mIm+][Br?] micelle is ellipsoidal, not spherical, in solutions over the C IL range examined here. 相似文献
122.
Tetsuo Sakamoto Kenji Ohishi Shun‐ichi Hayashi Masaaki Fujii 《Surface and interface analysis : SIA》2013,45(8):1309-1312
Aiming for the highly sensitive analysis of aromatic hydrocarbons in organic mixtures, selective ionization using an ultraviolet laser ionization technique was examined for the determination of sputtered neutral species on organic surfaces. The mass spectrum of a model mixture containing pyrene and n‐alkane showed that only pyrene was ionized and detected, whereas a mass spectrum without laser irradiation, i.e. in the case of secondary ion mass spectrometry, was dominated by many n‐alkane fragment peaks. This technique was applied for the detection of polyaromatic hydrocarbons adsorbed on diesel exhaust particles. Two kinds of polyaromatic hydrocarbons were clearly detected because many aliphatic fragment signals were suppressed by means of ultraviolet laser ionization. Copyright © 2013 John Wiley & Sons, Ltd. 相似文献
123.
Toshiyuki Fujii Frédéric Moynier Arnaud Agranier Emmanuel Ponzevera Minori Abe Akihiro Uehara Hajimu Yamana 《Journal of Radioanalytical and Nuclear Chemistry》2013,296(1):261-265
Environmental transport of Tl is affected by redox reaction between Tl(I) and Tl(III) and ligand exchange reactions of them. In order to deepen the knowledge of Tl chemistry, we investigated fractionation of Tl stable isotopes (203Tl and 205Tl) in a chemical exchange system. Tl isotopes were fractionated in a liquid–liquid extraction system, in which aqueous and organic phases are hydrochloric acid solution and dichloroethane including a crown ether, respectively. After purification by ion-exchange chemistry, the isotope ratio of 205Tl/203Tl in equilibrated aqueous phase was measured precisely by multiple-collector–inductively-coupled-plasma–mass-spectrometry. A large isotope fractionation >1 ‰ was found. Electronic structures of possible Tl species (hydrated Tl+, Tl3+, and Tl chlorides) were calculated by ab initio methods, and the isotope fractionation factor was theoretically obtained. The isotope fractionation via intramolecular vibrations was calculated to be much smaller than the experimental result. The isotope fractionation via isotopic change in nuclear volume, named the nuclear field shift effect, was calculated to be >1 ‰ in Tl(I)–Tl(III) redox systems and/or ligand exchange systems of Tl(III). The nuclear field shift effect was found to be the major origin of Tl isotope fractionation. 相似文献
124.
In this paper, we propose a method to accelerate the crystallisation of nematic liquid crystal mixtures based on crystallisation theory. This method is to hold a nematic liquid crystal sample at a temperature suitable for crystal growth after aging it at a temperature suitable for nucleation. After we specified these temperatures of a nematic liquid crystal mixture using differential scanning calorimetry, we demonstrate that the two-temperature aging method is effective for the crystallisation of other nematic liquid crystal mixtures in which the crystal-liquid crystal transition temperature has so far been undetectable. 相似文献
125.
Dr. Jun‐ichi Ito Kohei Fujii Prof. Dr. Hisao Nishiyama 《Chemistry (Weinheim an der Bergstrasse, Germany)》2013,19(2):601-605
NCN‐pincer Ru‐complexes containing bis(oxazolinyl)phenyl ligands serve as suitable catalysts in the direct conjugate additions of α,β‐unsaturated carbonyl compounds, including ketones, esters, and amides, as well as vinylphosphonates, giving various β‐alkynyl carbonyl and phosphonate compounds. A bis(oxazolinyl)phenyl (phebox)–Ru complex also catalyzes the asymmetric conjugate addition of an alkyne with a β‐substituted, α,β‐unsaturated ketone to produce a chiral β‐alkynyl ketone. 相似文献
126.
Tomohito Morosaki Tsubasa Suzuki Wei‐Wei Wang Shigeru Nagase Takayoshi Fujii 《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2014,126(36):9723-9725
Electronic effects on the central carbon atom of carbone, generated by the replacement of the SIV ligand of carbodisulfane (CDS) with other chalcogen ligands (Ph2E, E=S or Se), were investigated. The carbones Ph2E→C←SPh2(NMe) [E=S( 1 ) or Se( 2 )] were synthesized from the corresponding salts, and their molecular structures and electronic properties were characterized. The carbone 2 is the first carbone containing selenium as the coordinated atom. DFT calculations revealed the electronic structures of 1 and 2 , which have two lone pairs of electrons at the carbon center. The trend in HOMO energy levels, estimated by cyclic voltammetry measurements, for the carbones and CDS follows the order of 2 > 1 >CDS. Analysis of a doubly protonated dication and trication complex revealed that the central carbon atom of 2 behaves as a four‐electron donor. 相似文献
127.
Diversity oriented synthesis of conjugate dienes and alkenylcyclopropanes by the sequential reactions using silyl group-substituted titanium carbene complexes was studied. Dienylsilanes were obtained by the olefination of carbonyl compounds with γ-silylvinylcarbene complexes. Cyclopropanation of 1-alkenes with the vinylcarbene complexes produced (E)-(β-silylvinyl)cyclopropanes with high stereoselectivity. The reaction of β-(trialkylsilyl)carbene complexes with zinc alkoxides of homopropargyl alcohols produced 6-silyl-3,5-hexadien-1-ols with high regio- and stereoselectivity. The (E)-alkenylsilanes thus obtained were transformed into a range of unsaturated compounds by the palladium-catalyzed or copper(I)-promoted cross-coupling with organic halides with retention of configuration. 相似文献
128.
Xiaolei Wang Miho Emoto Atsushi Sugimoto Yusuke Miyake Kaori Itto Mitsuo Amasaka Shu Xu Hiroshi Hirata Hirotada Fujii Hirokazu Arimoto 《Tetrahedron letters》2014
A scalable synthetic route for 15N-labeled 4-oxo-2,2,6,6-tetraethylpiperidine nitroxide (15N-TEEPONE) is described. This 15N-labeled nitroxide is suitable for electron paramagnetic resonance imaging of brain, and its higher sensitivity compared with that of its 14N-counterpart is an important advantage of the labeled derivative. 相似文献
129.
130.
Kawada Y Hirata H Fujii H 《Journal of magnetic resonance (San Diego, Calif. : 1997)》2007,184(1):29-38
This article reports experimental investigations on the use of RF resonators for continuous-wave electron paramagnetic resonance (cw-EPR) and proton nuclear magnetic resonance (NMR) imaging. We developed a composite resonator system with multi-coil parallel-gap resonators for co-registration EPR/NMR imaging. The resonance frequencies of each resonator were 21.8MHz for NMR and 670MHz for EPR. A smaller resonator (22mm in diameter) for use in EPR was placed coaxially in a larger resonator (40mm in diameter) for use in NMR. RF magnetic fields in the composite resonator system were visualized by measuring a homogeneous 4-hydroxy-2,2,6,6-tetramethyl-piperidinooxy (4-hydroxy-TEMPO) solution in a test tube. A phantom of five tubes containing distilled water and 4-hydroxy-TEMPO solution was also measured to demonstrate the potential usefulness of this composite resonator system in biomedical science. An image of unpaired electrons was obtained for 4-hydroxy-TEMPO in three tubes, and was successfully mapped on the proton image for five tubes. Technical problems in the implementation of a composite resonator system are discussed with regard to co-registration EPR/NMR imaging for animal experiments. 相似文献