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Munetaka Takeuchi Yasuo Kameda Yasuhiro Umebayashi Sari Ogawa Takaaki Sonoda Shin-ichi Ishiguro Miho Fujita Mitsuru Sano 《Journal of Molecular Liquids》2009,148(2-3):99-108
Self-diffusion coefficients of Li+ DLi+, PF6− DPF6− and solvent propylene carbonate (PC) DPC in LiPF6−PC solutions were determined at 298 K by the pulse gradient spin echo (PGSE) NMR technique over the salt concentration range of 0.1–3.0 M (M = mol dm– 3). The order of the diffusion coefficients was found to be DLi+ < DPF6− < DPC over the concentration range examined, and they were monotonically decreased with increasing the salt concentration. Haven ratio Λ/ΛNMR, where Λ and ΛNMR represent the ionic conductivity measured electrochemically and that estimated via the Nernst-Einstein equation using the diffusion coefficient, respectively, was evaluated as the measure of the ion–ion interaction in the LiPF6–PC solutions. Though Λ/ΛNMR values for LiPF6-solutions decrease with increasing the salt concentration, they were greater than those for LiBF4–PC solutions over the whole concentration range examined, which indicates that the ion pair formation ability of PF6– ion is weaker than that of the BF4– ion. The smaller value of the ionic conductivity for the highly concentrated LiPF6–PC solution (above 2.0 M) than that of the LiBF4-solutions can be attributed to the more rapidly increased viscosity relative to the LiBF4-solution. Classic molecular dynamics (MD) simulations for the respective LiPF6 and LiBF4-solution of 0.5 and 1.0 M were also carried out based on the effective pair potentials. Diffusion coefficients, ionic conductivity and Haven ratio for these solutions were calculated from MD trajectories, and they qualitatively agree with those evaluated by experiments. Pair correlation functions gLiO(r) (for Li+–O (PC) pair) and gLiPF6(r) (for Li+–PF6– pair) or gLiBF4(r) (for Li+–BF4– pair) revealed that the lithium ion weakly forms the contact ion pairs with PF6–, whilst strongly with BF4–, which supports the present experimental results. Moreover, the simulation results show that both anions in the contact ion pairs predominantly take the monodentate form, which is in contrast to the multidentate coordination predicted by ab initio calculation in gas phase. 相似文献
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Miho Tanaka Kazuya Takahashi Tatsuya Urabe Tomohiro Oikawa Masao Nemoto Hideki Nagashima 《Rapid communications in mass spectrometry : RCM》2009,23(5):698-704
Silica, represented by SiO2, is the general name for the compounds composed of Si, O and H with their derivative complexes. Silica forms various chemical species in aquatic solutions, such as a monomer (Si(OH)3O−), dimer (Si2(OH)5O), and others. These species are known to vary in their relative abundances in solution depending on the chemical and physical conditions. Silica species dissolved in seawater have been examined by fast-atom bombardment mass spectrometry (FAB-MS) to elucidate the behavior of silica and its circulation as a novel tracer reflecting the chemical and physical conditions of seawater and the bioactivity of diatoms, which take up silica. In the seawater of Tokyo Bay, silica species such as [Si(OH)2O2Na]− ([monomer–Na]−), [Si2(OH)5O2]− ([dimer]−), [Si2(OH)4O3Na]− ([dimer–Na]−), [Si4(OH)7O5]− ([cyclic tetramer]−), [Si4(OH)6O6Na]− ([cyclic tetramer–Na]−), [Si4(OH)9O4]− ([linear tetramer]−) and [Si4(OH)8O5Na]− ([linear tetramer–Na]−) were observed and assigned by FAB-MS. To investigate the suitability of silica species as a tracer, the relative peak intensity ratios of silica species observed in the mass spectra, i.e. the profiles of the ratio of the linear tetramer to the cyclic tetramer (m/z 329/311) and the ratio of the dimer to the cyclic tetramer (m/z 173/311) against depth, were examined to determine the annual changes and reproducibility of the depth profiles. In particular, the depth profile of the relative ratio of the linear tetramer to the cyclic tetramer, 329/311, exhibits critical changes depending on the seawater budget. These changes in the relative ratios were identified by an experiment involving a simple sodium chloride solution system. Our measurement is expected to elucidate the dynamics of silica and its role as ‘food’ for diatoms, and we showed that speciation using mass spectrometry is a powerful tool for examining elemental behavior in nature and environmental changes. Our results suggest that a silica tracer is useful for investigating the behavior of seawater in small coastal regions and the uptake of silica by diatoms. Copyright © 2009 John Wiley & Sons, Ltd. 相似文献
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To study the interaction between liposomes and proteins, intact liposomes were immobilized on a metal planar support by chemical binding and/or bioaffinity using a quartz crystal microbalance (QCM). A large decrease in the resonance frequency of quartz crystal was observed when the QCM, modified by a self-assembled monolayer (SAM) of carboxythiol, was added to liposome solutions. The stable chemical immobilization of intact liposomes onto SAM was judged according to the degree with which adsorbed mass depended on the prepared size of liposomes, as well as on the activation time of SAMs when amino-coupling was introduced, where the liposome coverage of electrodes was 69+/-8% in optimal conditions. When avidin-biotin binding was used on amino-coupling liposome layers, liposome immobilization finally reached 168% coverage of the electrode surface. Denatured protein was also successfully detected according to the change in the frequency of the liposome-immobilized QCM. The adsorbed mass of denatured carbonic anhydrase from bovine onto immobilized liposomes showed a characteristic peak at a concentration of guanidine hydrochloride that corresponded to a molten globule-like state of the protein, although the mass adsorbed onto deactivated SAM increased monotonously. 相似文献
68.
We report nanosize-induced hydrogen storage in Ir, which does not absorb hydrogen in its bulk form. The mean diameter of the obtained Ir nanoparticles was estimated as 1.5 ± 0.5 nm by transmission electron microscopy. Hydrogen storage was confirmed by solid-state (2)H NMR and hydrogen pressure-composition isotherm measurements. 相似文献
69.
Diguet A Yanagisawa M Liu YJ Brun E Abadie S Rudiuk S Baigl D 《Journal of the American Chemical Society》2012,134(10):4898-4904
We study the behavior of multicomponent giant unilamellar vesicles (GUVs) in the presence of AzoTAB, a photosensitive surfactant. GUVs are made of an equimolar ratio of dioleoylphosphatidylcholine (DOPC) and dipalmitoylphosphatidylcholine (DPPC) and various amounts of cholesterol (Chol), where the lipid membrane shows a phase separation into a DPPC-rich liquid-ordered (L(o)) phase and a DOPC-rich liquid-disordered (L(d)) phase. We find that UV illumination at 365 nm for 1 s induces the bursting of a significant fraction of the GUV population. The percentage of UV-induced disrupted vesicles, called bursting rate (Y(burst)), increases with an increase in [AzoTAB] and depends on [Chol] in a non-monotonous manner. Y(burst) decreases when [Chol] increases from 0 to 10 mol % and then increases with a further increase in [Chol], which can be correlated with the phase composition of the membrane. We show that Y(burst) increases with the appearance of solid domains ([Chol] = 0) or with an increase in area fraction of L(o) phase (with increasing [Chol] ≥ 10 mol %). Under our conditions (UV illumination at 365 nm for 1 s), maximal bursting efficiency (Y(burst) = 53%) is obtained for [AzoTAB] = 1 mM and [Chol] = 40 mol %. Finally, by restricting the illumination area, we demonstrate the first selective UV-induced bursting of individual target GUVs. These results show a new method to probe biomembrane mechanical properties using light as well as pave the way for novel strategies of light-induced drug delivery. 相似文献
70.
Maity P Wakabayashi T Ichikuni N Tsunoyama H Xie S Yamauchi M Tsukuda T 《Chemical communications (Cambridge, England)》2012,48(49):6085-6087
Organogold clusters Au(54)(C(2)Ph)(26) were selectively synthesized by reacting polymer-stabilized Au clusters (1.2 ± 0.2 nm) with excess phenylacetylene in chloroform. 相似文献