津田 哲哉

A new group of ionic liquids based on tetraethylphosphonium and tetrabutylphosphonium cations together with several carboxylate anions is proposed and presented in this report. In obtained ionic liquids, tetrabutylphosphonium formate and tetrabutylphosphonium lactate became room temperature ionic liquids. It was found that the phosphonium ionic liquids showed the typical VTF-type convex curve behaviors. The phosphonium ionic liquids also had a high cathodic stability similar to those of the TFSA- and FSA-anion based phosphonium ionic liquids. On the other hand, relatively low anodic potential window was observed. The thermal stability of the phosphonium ionic liquids showed higher thermal stabilities than those of the corresponding ammonium ionic liquids.

A comprehensive understanding of the charge/discharge behaviour of high-capacity anode active materials, e.g., Si and Li, is essential for the design and development of next-generation high-performance Li-based batteries. Here, we demonstrate the in situ scanning electron microscopy (in situ SEM) of Si anodes in a configuration analogous to actual lithium-ion batteries (LIBs) with an ionic liquid (IL) that is expected to be a functional LIB electrolyte in the future. We discovered that variations in the morphology of Si active materials during charge/discharge processes is strongly dependent on their size and shape. Even the diffusion of atomic Li into Si materials can be visualized using a back-scattering electron imaging technique. The electrode reactions were successfully recorded as video clips. This in situ SEM technique can simultaneously provide useful data on, for example, morphological variations and elemental distributions, as well as electrochemical data.

Pt nanoparticles monodispersed in an ionic liquid (IL), which can be readily prepared by magnetron sputtering onto an IL, are a key material for tailoring highly durable Pt nanoparticle-supported carbon electrocatalysts, e.g., Pt nanoparticle-supported single-walled carbon nanotubes (Pt-SWCNTs) and Vulcan (R) XC-72 (Pt-Vulcan (R)), for the electrochemical oxygen reduction reaction. The durability largely surpasses that of one of the commercially available Vulcan (R) XC-72-based catalysts, TEC10V30E. The differences were very obvious from the results of electrochemical measurements, ex situ TEM observation, and in situ SEM/STEM observation; that is, considerable damage by carbon corrosion was recognized for the TEC10V30E, but it was not the case for the Pt-SWCNT and Pt-Vulcan (R). The unexpected high durability should be due to the suppression of carbon corrosion by the ionic liquid thin layer that exists between the Pt nanoparticles and carbon support.

A polymer gel electrolyte using AlCl3 complexed acrylamide as a functional monomer and acidic ionic liquid based on a mixture of 1-ethyl-3-methylimidazolium chloride (EMImCl) and AlCl3 (EMImCl-AlCl3, 1-1.5, in molar ratio) as a plasticizer has been successfully prepared for the first time via free radical polymerization. Aluminum deposition is successfully achieved using a polymer gel electrolyte containing 80 wt% ionic liquid. The polymer gel electrolytes are also good candidates for rechargeable aluminum ion batteries.

Electropolymerizable carbazole-functionalized imidazolium and pyridinium-based ionic liquids (ILs) were synthesized and characterized using H-1, C-13, F-19 NMR, and ESI-MS. They were electropolymerized onto indium tinoxide (ITO) electrodes via cyclic voltammetric polymerization in several selected room temperature ILs (RTILs) as well as in conventional organic solvents. Two redox couples, corresponding to the monomer and polymer, respectively, of the carbazole-functionalized ILs, were observed during the cyclic voltammetric polymerization. It was found, as common ILs, that the anionic components exhibit crucial effects on the physicochemical properties of the carbazole-functionalized ILs. The anions of which were replaced by the anions of the electrolytes in which the monomers were dissolved. The RTILs used for the electropolymerization thus determined the electrochemical behavior of the monomers, the surface morphologies and the physicochemical properties of the poly(ILs) films. After the modification of ITO electrodes with poly(ILs), the electrochemical performance of the semiconducting electrodes was significantly improved towards uric acid oxidation. The poly(ILs) show adjustable properties (via counter anions), and exhibit a wide range of solubility in organic solvents, and electrochromic and solvatochromic properties.

Aryltrifluoroborate ([ArBF3](-)) has a designable basic anion structure. Various [ArBF3](-)-based anions were synthesized to create novel alkali metal salts using a simple and safe process. Nearly 40 novel alkali metal salts were successfully obtained, and their physicochemical characteristics, particularly their thermal properties, were elucidated. These salts have lower melting points than those of simple inorganic alkali halide salts, such as KCl and LiCl, because of the weaker interactions between the alkali metal cations and the [ArBF3](-) anions and the anions' larger entropy. Moreover, interestingly, potassium cations were electrochemically reduced in the potassium (meta-ethoxyphenyl)trifluoroborate (K[m-OEtC6H4BF3]) molten salt at 433 K. These findings contribute substantially to furthering molten salt chemistry, ionic liquid chemistry, and electrochemistry.

The small spin-orbit interaction of carbon atoms in graphene promises a long spin diffusion length and the potential to create a spin field-effect transistor. However, for this reason, graphene was largely overlooked as a possible spin-charge conversion material. We report electric gate tuning of the spin-charge conversion voltage signal in single-layer graphene. Using spin pumping from an yttrium iron garnet ferrimagnetic insulator and ionic liquid top gate, we determined that the inverse spin Hall effect is the dominant spin-charge conversion mechanism in single-layer graphene. From the gate dependence of the electromotive force we showed the dominance of the intrinsic over Rashba spin-orbit interaction, a long-standing question in graphene research.

Scanning electron microscopy (SEM) has been successfully used to image biofilms because of its high resolution and magnification. However, conventional SEM requires dehydration and metal coating of biological samples before observation, and because biofilms consist mainly of water, sample dehydration may influence the biofilm structure. When coated with an ionic liquid, which is a kind of salt that exists in the liquid state at room temperature, biological samples for SEM observation do not require dehydration or metal coating because ionic liquids do not evaporate under vacuum conditions and are electrically conductive. This study investigates the ability of ionic liquids to allow SEM observation of Streptococcus mutans biofilms compared with conventional coating methods. Two hydrophilic and two hydrophobic ionic liquids, all of which are electronic conductors, are used. Compared with samples prepared by the conventional method, the ionic-liquid-treated samples do not exhibit a fibrous extracellular matrix structure and cracking on the biofilm surface. The hydrophilic ionic liquids give clearer images of the biofilm structure than those of the hydrophobic ionic liquids. This study finds that ionic liquids are useful for allowing the observation of biofilms by SEM without preparation by dehydration and metal coating.

The surface coating of metal nanoparticles resulting into core-shell structures is expected to improve the physicochemical properties of the nanoparticle cores without changing their size and shape. Here, we developed a novel strategy to coat Au, AuPd or Pt catalyst cores having average sizes smaller than 2.5 nm, which were pre-synthesized in ionic liquids by corresponding metal sputtering, with an extremely thin In2O3 layer (ca. <1.5 nm) by sputter deposition of indium in a room-temperature ionic liquid. The metal cores of Au or AuPd in core-shell particles exhibited superior stability against heat treatments or during electrocatalytic reactions compared to the corresponding bare metal particles. The In2O3 shell coating considerably enhanced the durability of electrocatalytically active Pt particles (1.2 nm). This sequential metal sputter deposition of different metals in ionic liquids will considerably contribute to the exploitation of key nanostructured components for next-generation energy-conversion systems.

A new silver micropatterning method has been developed by electron beam irradiation to room-temperature ionic liquid containing silver salts. This is the first achievement that uses liquid media to obtain metal deposits by electron beam lithography. Silver deposits were obtained as designed with high resolution and purity compared to the existing direct writing method.

Polyacrylonitrile-derived carbon particles with uniform size and high porosity were synthesized and their capacitor properties were investigated. The carbon particles were simply prepared just by carbonizing and activating monodisperse polyacrylonitrile particles which were synthesized by polymerization of acrylonitrile in the mixture of methanol and N,N-dimethylformamide. The electrochemical measurements revealed that the carbon particles electrode maintained large specific capacitance even at high charge-discharge current densities. (C) The Electrochemical Society of Japan, All rights reserved.

A new ionic liquid (IL) based on a "neutral" ligand, 4-propylpyridine, is obtained via complexation with AlCl3. It is found that the asymmetric cleavage of AlCl3 generates AlCl2+ and AlCl4, and the former is coordinated by 4-propylpyridine to produce the Al-containing cations ([AlCl2(4-Pr-Py)(2)](+)). The AlCl3/4-propylpyridine IL with a molar ratio of 1.3/1 is highly fluidic with a viscosity of 42.8 mPa s and an ionic conductivity of 5.0 x 10 x S-4/cm at room temperature. In contrast to conventional ILs for electroplating aluminum in which the electrochemically active species are Al-containing anions (for example Al2Cl7), this new IL has an Al-containing cation as the electroactive species, which is beneficial to electrodeposition of aluminum. (C) 2015 Elsevier Ltd. All rights reserved.

Metal fluoroanions are of significant interest for fundamental structure and reactivity studies and for making isotope ratio measurements that are free from isobaric overlap. Iron fluoroanions [FeF4](-) and [FeF3](-) were generated by electrospray ionization of solutions of Fe(III) and Fe(II) with the fluorinating ionic liquid 1-ethyl-3-methylimidazolium fluorohydrogenate [EMIm](+)[F(HF)(2.3)](-). Solutions containing Fe(III) salts produce predominately uncomplexed [FeF4](-) in the negative ion spectrum, as do solutions containing salts of Fe(II). This behavior contrasts with that of solutions of FeCl3 and FeCl2 (without [EMIm](+)[F(HF)(2.3)](-)) that preserve the solution-phase oxidation state by producing the gas-phase halide complexes [FeCl4](-) and [FeCl3](-), respectively. Thus, the electrospray-[EMIm](+)[F(HF)(2.3)](-) process is oxidative with respect to Fe(II). The positive ion spectra of Fe with [EMIm](+)[F(HF)(2.3)](-) displays cluster ions having the general formula [EMIm](+) ((n+1))[FeF4](-) (n), and DFT calculations predict stable complexes, both of which substantiate the conclusion that [FeF4](-) is present in solution stabilized by the imidazolium cation. The negative ion ESI mass spectrum of the Fe-ionic liquid solution has a very low background in the region of the [FeF4](-) complex, and isotope ratios measured for both [FeF4](-) and adventitious [SiF5](-) produced values in close agreement with theoretical values; this suggests that very wide isotope ratio measurements should be attainable with good accuracy and precision when the ion formation scheme is implemented on a dedicated isotope ratio mass spectrometer.

The cellular uptake of biodegradable particles as drug or vaccine carriers was observed by scanning electron microscopy employing an ionic liquid. The samples were observed by simply dipping them into the ionic liquid, and high-resolution images (sub-nanometer order) were achieved. The cellular uptake of polymeric nanoparticles (NPs) composed of biodegradable amphiphilic polymers was observed using an ionic liquid method for the first time. In particular, these NPs were observed when the quantum dots were immobilized on the NPs. In addition, when the cells were incubated with microparticles (MPs), the filopodia that covered the MPs were observed, and the cellular uptake of the MPs was evaluated in a time-dependent manner. This ionic liquid method is a promising technique for evaluating the cellular uptake behavior of drug or vaccine carriers. This method also provides a strategy for observing carriers that are sensitive to conventional pretreatment conditions by choosing a suitable ionic liquid.

By exploiting characteristics such as negligible vapour pressure and ion-conductive nature of an ionic liquid (IL), we established an in situ scanning electron microscope (SEM) method to observe the electrode reaction in the IL-based Li-ion secondary battery (LIB). When 1-ethyl-3-methylimidazolium bis(fluorosulfonyl)amide ([C(2)mim][FSA]) with lithium bis(trifluoromethanesulfonyl) amide (Li[TFSA]) was used as the electrolyte, the Si negative electrode exhibited a clear morphology change during the charge process, without any solid electrolyte interphase (SEI) layer formation, while in the discharge process, the appearance was slightly changed, suggesting that a morphology change is irreversible in the charge-discharge process. On the other hand, the use of 1-ethyl-3-methylimidazolium bis(trifluoromethanesulfonyl) amide ([C(2)mim][TFSA]) with Li[TFSA] did not induce a change in the Si negative electrode. It is interesting to note this distinct contrast, which could be attributed to SEI layer formation from the electrochemical breakdown of [C(2)mim](+) at the Si negative electrode vertical bar separator interface in the [C(2)mim][TFSA]based LIB. This in situ SEM observation technique could reveal the effect of the IL species electron-microscopically on the Si negative electrode reaction.

A novel method for fabricating microsized and nanosized polymer structures from a room-temperature ionic liquid (RTIL) on a Si substrate was developed by the patterned irradiation of an electron beam (EB). An extremely low vapor pressure of the RTIL, 1-allyl-3-ethylimidazolium bis((trifluoromethane)sulfonyl)amide, allows it to be introduced into the high-vacuum chamber of an electron beam apparatus to conduct a radiation-induced polymerization in the nanoregion. We prepared various three-dimensional (3D) micro/nanopolymer structures having high aspect ratios of up to 5 with a resolution of sub-100 nm. In addition, the effects of the irradiation dose and beam current on the physicochemical properties of the deposited polymers were investigated by recording the FT-IR spectra and Youngs modulus. Interestingly, the overall shapes of the obtained structures were different from those prepared in our recent study using a focused ion beam (FIB) even if the samples were irradiated in a similar manner. This may be due to the different transmission between the two types of beams as discussed on the basis of the theoretical calculations of the quantum beam trajectories. Perceptions obtained in this study provide facile preparation procedures for the micro/nanostructures.

The local structure within the CoFe atomic array of the photoswitchable coordination polymer magnet, K0.3Co[Fe(CN)(6)](0.77)center dot nH(2)O, is directly observed during charge transfer induced spin transition (CTIST), a solidsolid phase change, using high-resolution transmission electron microscopy (HRTEM). Along with the low-spin (LS) or thermally quenched high-spin (HS) states normally observed in CTIST solids at low temperature, slow cooling of K0.3Co[Fe(CN)(6)](0.77)center dot nH(2)O results in an intermediate phase containing both HS and LS domains with short coherence length. By mapping individual metalmetal distances, the nanometer-scale HS domains are directly visualized within the LS array. Temperature-dependent analyses allow monitoring of HS domain coarsening along the warming branch of the CTIST, providing direct visualization of the elastic process and insight into the mechanism of phase propagation. Normally sensitive to electron beam damage, the low-temperature TEM measurements of the porous coordination polymer are enabled by using appropriate ionic liquids instead of usual conductive thin-film coatings, an approach that should find general utility in related classes of materials.

Room-temperature ionic liquid (RTIL) is a liquid salt that can keep a liquid state over a wide range of temperature, and it possesses unique properties, for example, high thermal and chemical stabilities, relatively high ionic conductivity, wide electrochemical window, and extremely low vapor pressure. Of special note is that the peculiar liquid salt can be handled at 298K or less. Negligible vapor pressure of RTIL enables us to introduce RTIL in apparatuses requiring vacuum conditions, for example, electron microscope and sputtering system. This combination will make a contribution to the development of new techniques. In this article, with an eye on which RTIL has negligible vapor pressure, we have established novel analytical techniques combined with RTIL and a scanning electron microscope (SEM) system. Because of these successful achievements, we concluded that a RTIL-based SEM observation technique for biological specimens and in situ electrochemical reactions will be a useful technique for supporting the life sciences and for creating next-generation RTIL electrochemical devices.

Room-temperature ionic liquid (RTIL), which is a liquid salt at or below room temperature, shows peculiar physicochemical properties such as negligible vapor pressure and relatively-high ionic conductivity. In this investigation, we used six types of RTILs as a liquid material in the pretreatment process for scanning electron microscope (SEM) observation of hydrous superabsorbent polymer (SAP) particles. Very clear SEM images of the hydrous SAP particles were obtained if the neat RTILs were used for the pretreatment process. Of them, tri-n-butylmethylphosphonium dimethylphosphate ([P-4,P- 4,P- 4,P- 1][DMP]) provided the best result. On the other hand, the surface morphology of the hydrous SAP particles pretreated with 1-ethyl-3-methylimidazolium tetrafluoroborate ([C(2)mim][BF4]) and 1-butyl-3-methylimidazolium tetrafluoroborate ([C(4)mim][BF4]) was damaged. The results of SEM observation and thermogravimetry analysis of the hydrous SAP pretreated with the RTILs strongly suggested that most water in the SAP particles are replaced with RTIL during the pretreatment process.

We investigated the charge-discharge characteristics of the natural graphite negative electrode in N, N-diethyl-N-methyl-N-(2-methoxyethyl) ammonium bis (trifluoromethylsulfonyl) amide (DEME-TFSA) containing lithium ion as the electrolyte for nonflammable lithium-ion batteries. The charge-discharge tests showed that the discharge capacity was stably maintained at ca. 300 mAh g(-1) until the initial 10th cycle and the charge-discharge efficiencies reached ca. 100% after the initial cycles. The FE-SEM/EDX mapping results showed that the surface deposit (O, F, and S) deriving from DEME-TFSA was formed during the 1st charge. The XPS analysis results indicated that the surface deposit would compose of LiF, O, and S. It was found that the LiF-based compound containing O and S as a surface deposit was formed on the natural graphite electrode due to the cathodic decomposition of the TFSA-anion as a side reaction during the 1st charge.

Electrodeposited alloys are rarely in thermodynamic equilibrium, and several unique microstructural features such as extended solid solubility, metastable crystalline phases, and metallic glasses are generally observed. Because the excess free energy of the deposit is inversely proportional to the atomic mobility, phase constitution depends strongly on deposition temperature. This paper examines the influence of deposition temperature on the crystal structure of electrodeposited Al-Mn and Al-Ti alloys electrodeposited from AlCl3-NaCl and AlCl3-EMImCl ionic liquids from temperatures ranging from 80 degrees C to 425 degrees C. Deposition at low temperature favors the preferential deposition of amorphous and crystalline phases which appear as high temperature variants in the equilibrium phase diagram. These structures generally have high symmetry, and for this reason are relatively easy to nucleate. The room temperature equilibrium phases, which generally have a more complicated structure, can only be obtained at elevated deposition temperatures.

Aromatic trifluoroborate ([Ar-BF3](-)) is a useful anion structure for molten salt and ionic liquid (IL) designing because we can attach various sorts of substituents on the aromatic ring with ease. A number of alkali metal salts having [Ar-BF3](-) were synthesized and their physical properties were measured. The salts showed lower melting point than simple inorganic salt, e.g., KCl and LiCl. When phenyltrifluoroborate ([PhBF3](-)) and 1-ethyl-3-methylimidazolium ([C(2)mim](+)) or 1-butyl-3-methylimidazolium ([C(4)mim](+)) were combined, the resulting salts became a liquid state at room temperature. These ILs exhibited favorable viscosity and ionic conductivity comparable to a typical IL species, [C(4)mim][BF4].

Pt nanoparticles dispersed in room temperature ionic liquid (RTIL) can easily be prepared by metal-sputtering onto RTIL. When the prepared Pt nanoparticles-dispersed RTIL is put on a glassy carbon (GC) plate or mixed with single wall carbon nanotubes (SWCNTs) while being heated, adsorption of Pt nanoparticles on the carbon surfaces is induced. Both resulting Pt nanoparticles-adsorbed GC and SWCNT exhibit distinct electrocatalytic activity toward oxygen reduction reaction.

The electrodeposition of non-equilibrium ternary Al-W-Mn alloys was investigated in the Lewis acidic 66.7-33.3 mol % aluminum chloride-1-ethyl-3-methylimidazolium chloride (AlCl3-[C(2)mim]Cl) ionic liquid (IL) with K-3[W2Cl9] and MnCl2 to improve the properties of binary Al-W alloy electrodeposits. The Al-W-Mn alloys were electrochemically deposited on Cu substrates. The W content in the Al-W-Mn alloys monotonically decreased with increasing the applied current density independently of the K-3[W2Cl9] and MnCl2 concentration in the IL solution. The Mn content in the ternary alloys was significantly affected by the electrodeposition condition. The XRD and EDS analyses revealed that the Al-W-Mn alloys prepared in this research have non-equilibrium solid solution and amorphous phases without chloride contamination. The surface morphology was improved by adding Mn to the Al-W alloy, and the pitting potential of the Al-W-Mn alloy surpassed that for the electrodeposited Al-W and Al-Mn binary alloy systems.

A new type of electrochemical cell was developed for in situ transmission electron microscopy observation that enables the electrode materials to be conveniently changed. The electrochemical cell was used to observe the electrochemical growth or dissolution of copper islands on a gold film with simultaneous cyclic voltammetry measurements. The copper islands could be explained by three-dimensional growing model.

Recent advances in in situ transmission electron microscopy (TEM) techniques have provided unprecedented knowledge of chemical reactions from a microscopic viewpoint. To introduce volatile liquids, in which chemical reactions take place, use of sophisticated tailor-made fluid cells is a usual method. Herein, a very simple method is presented, which takes advantage of nonvolatile ionic liquids without any fluid cell. This method is successfully employed to investigate the essential steps in the generation of gold nanoparticles as well as the growth kinetics of individual particles. The ionic liquids that we select do not exhibit any anomalous effects on the reaction process as compared with recent in situ TEM studies using conventional solvents. Thus, obtained TEM movies largely support not only classical theory of nanoparticle generation but also some nonconventional phenomena that have been expected recently by some researchers. More noteworthy is the clear observation of lattice fringes by high-resolution TEM even in the ionic liquid media, providing intriguing information correlating coalescence with crystal states. The relaxation of nanoparticle shape and crystal structure after the coalescence is investigated in detail. The effect of crystal orientation upon coalescence is also analyzed and discussed.

In this study, an ionic liquid-Fe3O4 nanoparticles-graphite composite electrode (IL-Fe3O4NPd-GP) with high sensitivity was fabricated using easy-to-made materials and convenient techniques. A hydrophobic ionic liquid 1-butyl-1-methylpyrrolidinium bis((trifluoromethyl)sulfonyl)amide (IL BMP-TFSA) was used to substitute paraffin oil that is conventionally used as the organic binder for preparing carbon paste electrodes. Fe3O4NPd show pseudo-peroxidase activity toward hydrogen peroxide (H2O2) that was electrocatalytically reduced at the electrode. This electrode shows the synergistic effect from the combination of IL and Fe3O4NPd, exhibiting a high sensitivity of 200.7}LA mM(-1) cm(-2) but a narrower dynamic range of 1-25 mu M with a detection limit of 0.5 mu M. This electrode also shows good stability and several common interferents show negligible effect on the determination of H2O2. (C) 2014 Elsevier B.V. All rights reserved.

RATIONALE New approaches for forming anions are sought that have strong abundance and no isobaric overlap, attributes that are compatible with the measurement of isotope ratios. Fluoroanions are particularly attractive because fluorine is monoisotopic, and thus will not have overlapping isobars with the isotope of interest. Since many elements do not have positive electron affinity values, they do not form stable negative atomic ions, and hence are not compatible with isotope ratio measurement using high sensitivity isotope ratio mass spectrometers such as accelerator mass spectrometers. METHODS Zirconium fluoroanions were prepared using the fluorinating ionic liquid (IL) 1-ethyl-3-methylimidazolium fluorohydrogenate, which was used to generate abundant [ZrF5]- ions using electrospray ionization. The IL was dissolved in acetonitrile, combined with a dilute solution of either Zr4+ or ZrO2+, and then electrosprayed. Mass analysis and collision-induced dissociation experiments were conducted using a time-of-flight mass spectrometer. Cluster structures were predicted using density functional theory calculations. RESULTS The fluorohydrogenate IL solutions generated abundant [ZrF5]- ions starting from solutions of both Zr4+ and ZrO2+. The mass spectra also contained IL-bearing cluster ions, whose compositions indicated the presence of [ZrF6]2- in solution, a conclusion supported by the structural calculations. Rinsing out the zirconium-IL solution with acetonitrile decreased the IL clusters, but enhanced [ZrF5]-, which was sorbed by the polymeric electrospray supply capillary, and then released upon rinsing. This reduced the ion background in the mass spectrum. CONCLUSIONS The fluorohydrogenate-IL solutions are a facile way to form zirconium fluoroanions in the gas phase using electrospray. The approach has potential as a source of fluoroanions for isotope ratio measurements, which would enable high-sensitivity measurement of minor zirconium isotopes without overlapping isobars caused by the charge carrier (i.e., the monoisotopic fluorine atoms). Copyright (c) 2014 John Wiley & Sons, Ltd.

Room-temperature ionic liquid (RTIL) has been widely investigated as a nonvolatile solvent as well as a unique liquid material because of its interesting features, e. g., negligible vapor pressure and high thermal stability. Here we report that a non-volatile polymerizable RTIL is a useful starting material for the fabrication of micro/nano-scale polymer structures with a focused-ion-beam (FIB) system operated under high-vacuum condition. Gallium-ion beam irradiation to the polymerizable 1-allyl-3-ethylimidazolium bis((trifluoromethane) sulfonyl) amide RTIL layer spread on a Si wafer induced a polymerization reaction without difficulty. What is interesting to note is that we have succeeded in provoking the polymerization reaction anywhere on the Si wafer substrate by using FIB irradiation with a raster scanning mode. By this finding, two-and three-dimensional micro/nano-scale polymer structure fabrications were possible at the resolution of 500,000 dpi. Even intricate three-dimensional micro/nano-figures with overhang and hollow moieties could be constructed at the resolution of approximately 100 nm.

Now room-temperature ionic liquid (RTIL) is becoming a general term in the fields of science and technology owing to its useful physicochemical properties. A great number of applications with RTIL are proposed to date. Here we report an original electrochemical energy storage device with a Lewis acidic 60.0-40.0 mol% AlBr3-1-ethyl-3-methylimidazolioum bromide ([C(2)mim]Br) RTIL. The unique electrochemical reactions related to [AlBr4]-anion on the positive electrode have a crucial role in the energy storage device. The charge-discharge ratio for the beaker cell prepared in this investigation was almost 100% at 2.0 similar to 5.0 mA (150 similar to 370 mA g(-1) for activated carbon fiber cloth) if the cutoff voltage for the charging process was less than 1.70 V. The clear self-discharge behavior was not observed and the cell capacity after 100 cycles was identical to the maximum value. (C) The Author(s) 2014. Published by ECS.

The electrodeposition of non-equilibrium Al-W alloys was investigated in the Lewis acidic 66.7-33.3 percent mole fraction aluminum chloride-1-ethyl-3-methylimidazoliurn chloride (AlCl3-[EtMeIm]Cl) room-temperature ionic liquid (IL). The W(III) compound, K-3[W2Cl9], served as the reservoir for W. Both controlled potential and controlled current techniques were employed. Depending on the electrodeposition conditions, it was possible to prepare Al-W alloys with a W content approaching 96 percent atomic fraction (a/o). However, as the W content of these alloys increased above 30 a/o, the deposits became powdery and friable and were difficult to characterize. XRD analysis of deposits containing similar to 16 a/o W revealed a broad reflection consistent with the amorphous phase that typically appears at alloy concentrations that exceed the limit of the supersaturated solid solution. This phase is not readily apparent in X-ray diffraction patterns until the W content reaches about 9 a/o. As expected, the lattice parameter for the fcc Al phase decreased as the W content of the alloy increased, reaching a maximum contraction of about 0.2%, consistent with a W content of about 5 a/o. This suggests that the amorphous phase may be present in deposits containing a little as 5 a/o W. Alloys containing similar to 3 a/o W were dense and compact and displayed a chloride pitting potential of +0.3 V versus unalloyed Al. Heat treatment was explored as a method to address the powdery morphology of those deposits with a high W content, but XRD analysis indicated that this approach leads to the precipitation of at least one new phase (Al5W) and a decrease in the chloride pitting potential. (C) 2014 The Electrochemical Society. All rights reserved.

Ionic liquids (ILs) are room-temperature molten salts that have applications in both physical sciences and more recently in the purification of proteins and lipids, gene transfection and sample preparation for electron microscopy (EM) studies. Transfection of genes into cells requires membrane fusion between the cell membrane and the transfection reagent, thus, ILs may be induce a membrane fusion event. To clarify the behavior of ILs with cell membranes the effect of ILs on model membranes, i.e., liposomes, were investigated. We used two standard ILs, 1-ethyl-3-methylimidazolium lactate ([EMI][Lac]) and choline lactate ([Ch][Lac]), and focused on whether these ILs can induce lipid vesicle fusion. Fluorescence resonance energy transfer and dynamic light scattering were employed to determine whether the ILs induced vesicle fusion. Vesicle solutions at low IL concentrations showed negligible fusion when compared with the controls in the absence of ILs. At concentrations of 30% (v/v), both types of ILs induced vesicle fusion up to 1.3 and 1.6 times the fluorescence intensity of the control in the presence of [Ch][Lac] and [EMI] [Lac], respectively. This is the first demonstration that [EMI][Lac] and [Ch][Lac] induce vesicle fusion at high IL concentrations and this observation should have a significant influence on basic biophysical studies. Conversely, the ability to avoid vesicle fusion at low IL concentrations is clearly advantageous for EM studies of lipid samples and cells. This new information describing IL-lipid membrane interactions should impact EM observations examining cell morphology. © 2013 Hayakawa et al.

Electrospray ionization of the fluorohydrogenate ionic liquid [1-ethyl-3-methylimidazolium][F(HF)2.3] ionic liquid was conducted to understand the nature of the anionic species as they exist in the gas phase. Abundant fluorohydrogenate clusters were produced however, the dominant anion in the clusters was [FHF-], and not the fluoride-bound HF dimers or trimers that are seen in solution. Density functional theory (DFT) calculations suggest that HF molecules are bound to the clusters by about 30 kcal/mol. The DFT-calculated structures of the [FHF-]-bearing clusters show that the favored interactions of the anions are with the methynic and acetylenic hydrogen atoms on the imidazolium cation, forming planar structures similar to those observed in the solid state. A second series of abundant negative ions was also formed that contained [SiF5-] together with the imidazolium cation and the fluorohydrogenate anions that originate from reaction of the spray solution with silicate surfaces. © 2013 American Chemical Society.

Electrospray ionization of the fluorohydrogenate ionic liquid [1-ethyl-3-methylimidazolium][F(HF)2.3] ionic liquid was conducted to understand the nature of the anionic species as they exist in the gas phase. Abundant fluorohydrogenate clusters were produced however, the dominant anion in the clusters was [FHF-], and not the fluoride-bound HF dimers or trimers that are seen in solution. Density functional theory (DFT) calculations suggest that HF molecules are bound to the clusters by about 30 kcal/mol. The DFT-calculated structures of the [FHF-]-bearing clusters show that the favored interactions of the anions are with the methynic and acetylenic hydrogen atoms on the imidazolium cation, forming planar structures similar to those observed in the solid state. A second series of abundant negative ions was also formed that contained [SiF5-] together with the imidazolium cation and the fluorohydrogenate anions that originate from reaction of the spray solution with silicate surfaces. © 2013 American Chemical Society.

Electrospray ionization of the fluorohydrogenate ionic liquid [1-ethyl-3-methylimidazolium][F(HF)2.3] ionic liquid was conducted to understand the nature of the anionic species as they exist in the gas phase. Abundant fluorohydrogenate clusters were produced however, the dominant anion in the clusters was [FHF-], and not the fluoride-bound HF dimers or trimers that are seen in solution. Density functional theory (DFT) calculations suggest that HF molecules are bound to the clusters by about 30 kcal/mol. The DFT-calculated structures of the [FHF-]-bearing clusters show that the favored interactions of the anions are with the methynic and acetylenic hydrogen atoms on the imidazolium cation, forming planar structures similar to those observed in the solid state. A second series of abundant negative ions was also formed that contained [SiF5-] together with the imidazolium cation and the fluorohydrogenate anions that originate from reaction of the spray solution with silicate surfaces. © 2013 American Chemical Society.

The physicochemical properties of novel four tri-n-butylalkylphosphonium-based room-temperature ionic liquids (RTILs), tri-n-butylmethylphosphonium dimethylphosphate ([P-4,P-4,P-4,P-1][DMP]), tri-n-buty1(2-hydroxymethyl)phosphonium bis(trifluoromethylsulfonyl)amide ([P-4,P-4,P-4,P-2OH][Tf2N]), tetra-n-butylphosphonium O,O'diethylphosphorodithioate ([P-4,P-4,P-4,P-4][DEPDT]), and tri-n-butyldodecylphosphonium 3,5-bis(methoxycarbonyl)benzenesulfonate ([P-4,P-4,P-4,P-12][MCBS]), were examined in this study. All RTILs showed a favorable thermal decomposition temperature exceeding 560 K. Of these, [P-4,P-4,P-4,P-12][MCBS] exhibited a fairly high thermal stability compared with common phosphonium cation-based RTILs reported to date. Interestingly [P-4,P-4,P-4,P-1] [DMP] formed an ionic plastic crystal phase within a range of 279-290 K, but that was not the case with [P-4,P-4,P-4,P-4][DEPDT], which is similar in the cation and anion structures to the [P-4,P-4,P-4,P-1](+) and [DMP](-). [P-4,P-4,P-4,P-2OH][Tf2N] showed a relatively high conductivity of 0.48 mS cm(-1) at 303 K among the RTILs consisting of tri-n-butylalkylphosphonium cation and usual fluoroanion.

Transcellular Mg2+ transport across epithelia, involving both apical entry and basolateral extrusion, is essential for magnesium homeostasis, but molecules involved in basolateral extrusion have not yet been identified. Here, we show that CNNM4 is the basolaterally located Mg2+ extrusion molecule. CNNM4 is strongly expressed in intestinal epithelia and localizes to their basolateral membrane. CNNM4-knockout mice showed hypomagnesemia due to the intestinal malabsorption of magnesium, suggesting its role in Mg2+ extrusion to the inner parts of body. Imaging analyses revealed that CNNM4 can extrude Mg2+ by exchanging intracellular Mg2+ with extracellular Na+. Furthermore, CNNM4 mutations cause Jalili syndrome, characterized by recessive amelogenesis imperfecta with cone-rod dystrophy. CNNM4-knockout mice showed defective amelogenesis, and CNNM4 again localizes to the basolateral membrane of ameloblasts, the enamel-forming epithelial cells. Missense point mutations associated with the disease abolish the Mg2+ extrusion activity. These results demonstrate the crucial importance of Mg2+ extrusion by CNNM4 in organismal and topical regulation of magnesium.

Physicochemical data of the novel low-melting-point melt systems combining urea with the 1-alkyl-3-methylimidazolium chloride ([R1MeIm]Cl) were examined in order to produce an alternative to room-temperature ionic liquid that is very expensive to prepare and purify compared to the conventional molecular solvents. [HexMeIm]Cl- and [MeOctIm]Cl-rich urea melts, which have almost the same pyrolysis temperature as neat [HexMeIm]Cl and [MeOctIm]Cl organic salts, showed a stable liquid phase at room temperature. The various physicochemical properties of the [MeOctIm]Cl-rich urea room-temperature melts were measured as a function of temperature. The VTF equation was fitted to the conductivity and viscosity data, and a simple polynomial was fitted to the density data. Interestingly, although the 75.0-25.0 mol% [BuMeIm]Cl-urea melt did not give a stable liquid phase at room temperature, the melt showed favorable conductivity that exceeds that for the [MeOctIm]Cl-rich urea melts at the temperature exceeding 323 K. Further investigation on the applications, e.g., Cu electroplating, SEM observation technique, and Au nanoparticle preparation, using the [R1MeIm]Cl-urea melt system revealed that the melt system has a great possibility as an alternative to the RTIL. © 2012 Elsevier Ltd.

The direct electrolytic reduction of solid SiO2 is investigated in molten CaCl2 at 1123 K to produce solar-grade silicon. The target concentrations of impurities for the primary Si are calculated from the acceptable concentrations of impurities in solar-grade silicon (SOG-Si) and the segregation coefficients for the impurity elements. The concentrations of most metal impurities are significantly decreased below their target concentrations by using a quartz vessel and new types of SiO2-contacting electrodes. The electrolytic reduction rate is increased by improving an electron pathway from the lead material to the SiO2, which demonstrates that the characteristics of the electric contact are important factors affecting the reduction rate. Pellet-and basket-type electrodes are tested to improve the process volume for powdery and granular SiO2. Based on the purity of the Si product after melting, refining, and solidifying, the potential of the technology is discussed.

The electrochemistry of Hf(IV) and the electrodeposition of Al-Hf alloys were examined in the Lewis acidic 66.7-33.3 mol% aluminum chloride-1-ethyl-3-methylimidazolium chloride molten salt containing HfCl4. When cyclic staircase voltammetry was carried out at a platinum disk electrode in this melt, the deposition and stripping waves for Al shifted to negative and positive potentials, respectively, suggesting that aluminum stripping is more difficult due to the formation of Al-Hf alloys. Al-Hf alloy electrodeposits containing 13 at.% Hf were obtained on Cu rotating wire and cylinder electrodes. The Hf content in the Al-Hf alloy deposits depended on the HfCl4 concentration in the melt, the electrodeposition temperature, and the applied current density. The deposits were composed of dense crystals and were completely chloride-free. The chloride-induced pitting corrosion potential of the resulting Al-Hf alloys was approximately +0.30 V against pure aluminum when the Hf content was above 10 at.%.

イオン液体は，常温でも液体状態の塩である．蒸気圧が極端に小さいため，真空下でも蒸発することはない．そこで，イオン液体を走査型電子顕微鏡（SEM）の中に入れて観察したところ，全く帯電せずに観察することができた．この発見を契機に，イオン液体中で電気化学反応を行わせ，それをSEMによってその場で観察する方法の開発を行っている．その研究の流れと，観察方法の基本的な原理と技術を概説する．

The cellular uptake of nanoparticles (NPs) was clearly observed by scanning electron microscopy (SEM) employing an ionic liquid for the first time. The samples did not show charge-up effect without staining, and high contrast images were achieved. Because of these unique properties of the ionic liquid, we could finely observe the cellular uptake of NPs compared with conventional SEM observation method. Moreover, the cells became transparent as the accelerating voltage increased, and the internalized NPs composed of heavy atoms were easily determined. This ionic liquid method provides a simple and short pretreatment procedure and thus is a promising technique for evaluating the cellular uptake of NPs and the intracellular fate of NPs. This method also gives a strategy to observe NPs which are unstable in the dry condition by choosing a suitable ionic liquid. © 2013 The Chemical Society of Japan.

In situ SEM observation of a lithium deposition and dissolution process in an all-solid-state lithium metal battery using a sulfide-based solid electrolyte (SE) was carried out. We revealed visually that the morphology of lithium deposition varies with the operating current densities. At current densities higher than 1 mA cm(-2), local lithium deposition triggers large cracks, leading to a decrease in the reversibility of lithium deposition and dissolution. On the other hand, at a low current density of 0.01 mA cm(-2), its homogeneous deposition, which enables the reversible deposition and dissolution, hardly brings about the occurrence of unfavorable cracks. These results suggest that homogeneous lithium deposition on the SE and the suppression of the growth of lithium metal along the grain boundaries inside the SE are keys to achieve the repetitive lithium deposition and dissolution reaction without deterioration of the SE.