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461.
The rotational dynamics of benzene and water in the ionic liquid (IL) 1-butyl-3-methylimidazolium chloride are studied using molecular dynamics (MD) simulation and NMR T(1) measurements. MD trajectories based on an effective potential are used to calculate the (2)H NMR relaxation time, T(1) via Fourier transform of the relevant rotational time correlation function, C(2R)(t). To compensate for the lack of polarization in the standard fixed-charge modeling of the IL, an effective ionic charge, which is smaller than the elementary charge is employed. The simulation results are in closest agreement with NMR experiments with respect to the temperature and Larmor frequency dependencies of T(1) when an effective charge of ±0.5e is used for the anion and the cation, respectively. The computed C(2R)(t) of both solutes shows a bi-modal nature, comprised of an initial non-diffusive ps relaxation plus a long-time ns tail extending to the diffusive regime. Due to the latter component, the solute dynamics is not under the motional narrowing condition with respect to the prevalent Larmor frequency. It is shown that the diffusive tail of the C(2R)(t) is most important to understand frequency and temperature dependencies of T(1) in ILs. On the other hand, the effect of the initial ps relaxation is an increase of T(1) by a constant factor. This is equivalent to an "effective" reduction of the quadrupolar coupling constant (QCC). Thus, in the NMR T(1) analysis, the rotational time correlation function can be modeled analytically in the form of aexp (-t/τ) (Lipari-Szabo model), where the constant a, the Lipari-Szabo factor, contains the integrated contribution of the short-time relaxation and τ represents the relaxation time of the exponential (diffusive) tail. The Debye model is a special case of the Lipari-Szabo model with a = 1, and turns out to be inappropriate to represent benzene and water dynamics in ILs since a is as small as 0.1. The use of the Debye model would result in an underestimation of the QCC by a factor of 2-3 as a compensation for the neglect of the Lipari-Szabo factor. 相似文献
462.
Cadmium in polyethylene was determined by both inductively coupled plasma atomic emission spectrometry (ICP-AES) and atomic absorption spectrometry (AAS) with continuous-flow gas-phase sample introduction in a reaction medium of ascorbic acid. In the presence of mixture of cobalt and thiourea in the ascorbic acid solution, the sensitivities by both ICP-AES and AAS for cadmium were greatly enhanced. The gaseous cadmium species was phase-separated in a gas–liquid separator and directed via a stream of argon carrier gas to an inductively coupled plasma and an electrically heated quartz tube atomizer (QTA) for atomic spectrometry. Under the optimized experimental conditions, the best attainable detection limits at Cd I 228.802 nm line were 1.3 and 0.017 ng/ml with linear dynamic ranges of 10–500 ng/ml and 0.1–1 ng/ml in concentrations by ICP-AES and QTA-AAS, respectively. The instrumental precisions expressed as the relative standard deviation (R.S.D.) from ten replicate measurements of 50 and 1 ng/ml cadmium by ICP-AES and QTA-AAS were 5.6% and 3.2%, respectively. With the use of ICP-AES and QTA-AAS with gas-phase sample introduction method, six- and 200-fold improvements in detection limits for cadmium were obtained in comparison with their conventional solution nebulization methods, respectively. After the effects of several diverse elements on the determination of cadmium by ICP-AES and QTA-AAS with the present gas-phase sample introduction systems were examined, these methods were applied to the determination of low concentrations of cadmium in polyethylene. The results obtained by the present method were in good agreement with the certified values. 相似文献
463.
Hari Y Akabane M Hatanaka Y Nakahara M Obika S 《Chemical communications (Cambridge, England)》2011,47(15):4424-4426
In order to expand target sequences in triplex DNA formation, the development of a nucleobase that recognizes a CG base pair in dsDNA was attempted. A 4-[(3R,4R)-dihydroxypyrrolidino]pyrimidin-2-one nucleobase was found to recognize a CG base pair with high sequence-selectivity. 相似文献
464.
Yoshio Nakahara Tsutomu Takeuchi Shoutaro Yokoyama Keiichi Kimura 《Surface and interface analysis : SIA》2011,43(4):809-815
Quantitative analysis of reacted silanol groups in silica nanoparticles modified chemically with monochlorosilanes was performed by 1H NMR after treatment with cesium fluoride. Silica nanoparticles were modified chemically by the reaction between the silanol groups and monochlorosilanes, and the structure of the organic moiety anchored onto the silica surface was confirmed with solid‐state 13C NMR. As monochlorosilanes react with silanol groups at 1:1 ratio unlike di‐ or trichlorosilanes, the number of the silanes introduced into silica nanoparticles equals that of reacted silanol groups. Organically modified silica nanoparticles were dissolved using cesium fluoride, and the amount of the soluble organic compounds originated from the introduced silanes was determined by a 1H NMR internal standard method using pyrene as the reference. Those values determined by 1H NMR were in good agreement with those determined by elemental analysis. Thus, the number of reacted silanol groups per one particle was calculated on the basis of the results obtained by the 1H NMR method, and the values were highly dependent on the steric structure of the introduced silanes. Copyright © 2010 John Wiley & Sons, Ltd. 相似文献
465.
Simple and effective procedures for the determination of Re, Os and Ir by radiochemical neutron activation analysis are presented. Those elements are separated individually by distillation (for Os) and anion exchange techniques (for Re and Ir) for a single specimen. Reproducibilities of the data obtained by the present procedures are evaluated by replicate analyses of the Allende meteorite sample, and are deduced to be 3% for Re, 6% for Os and 4% for Ir (1). Detection limits for the present procedures are calculated to be 1 ppb for Re, 20 ppb for Os and 5 ppb for Ir. These procedures were applied to Antarctic meteorites and proved to work very effectively for the determination of trace Re, Os and Ir in chondrite meteorites. 相似文献
466.
Nakahara S Tanner DA Hudson S Magner E Redington W Hodnett K 《Physical chemistry chemical physics : PCCP》2011,13(3):1189-1200
A transmission electron microscope was used to characterize a powder form of hexagonally-ordered mesoporous silica material. The structural symmetry built into this amorphous material allowed one to obtain three characteristic images, i.e. a hexagonal honey-comb structure and wide/narrow parallel lines. These images were found to originate primarily from phase contrast, which changed sensitively with defocusing. To further understand the contrast behaviour of these images, an analytical form of the defocus contrast theory was developed and applied to the simulation of the characteristic wide/narrow parallel line images. The simulation was found to be in good qualitative agreement with experiments, where changes in focus conditions and specimen thickness were predicted to alter the contrast in the resulting parallel-line type images. 相似文献
467.
In the so-called thioester method for the condensation of peptide segments, protecting groups for amino and thiol groups are required for chemoselective ligation. In this study, we developed a novel thiol protecting group, N-methyl-phenacyloxycarbamidomethyl (Pocam). We used it for protection of cysteine side chains, and synthesized Pocam-containing peptides and peptide thioesters. These were condensed by the thioester method. After the condensation reaction, Pocam groups were cleaved by Zn/AcOH treatment. At the same time, the azido group, which was used for the protection of lysine side chains, was also converted to an amino group, demonstrating that this protecting group strategy simplified the deprotecting reaction after the peptide condensation reaction to only one step. 相似文献
468.
Giordani C Wakai C Okamura E Matubayasi N Nakahara M 《The journal of physical chemistry. B》2006,110(31):15205-15211
Self-diffusion coefficients (D) are measured for normal (nondeuterated) and deuterated cholesterol-d(6) (C26 and C27 methyl groups deuterated) in 1-octanol, chloroform, and cyclohexane at concentrations of 1-700 mM by varying the impurity water concentration (>2 mM) and temperature (30-50 degrees C). The pulsed field gradient spin-echo (PGSE) (1)H and (2)H NMR were used, respectively, at 600 and 92 MHz. At 30 degrees C, the hydrodynamic radius (R) obtained at 20 mM from the D value and solvent viscosity is 5.09, 7.07, and 6.17 A, respectively, in 1-octanol, chloroform, and cyclohexane when the impurity water is negligible. The R value in 1-octanol is the smallest and comparable with the average length of the molecular axes for the cholesterol molecule. In 1-octanol, R is invariant against the concentration variation, whereas in chloroform, R is larger and increases almost linearly with cholesterol concentration. At the highest concentration, 700 mM, the R in chloroform is 13.5 and 16.7 A, respectively, when the impurity water is at negligible and saturated concentrations. The R value larger than that in hydrogen-bonding 1-octanol indicates that cholesterol forms an aggregate through hydrogen bonding. The aggregate structure is confirmed by comparing NOESY spectra in chloroform and 1-octanol. The NOESY analysis reveals the presence of one extra cross peak (C4-C19) in chloroform compared to 1-octanol. Because the carbon atoms related to the cross peak are close to the hydroxyl group (C3-OH), cholesterol molecules are considered to be not piled but are found to be OH-centered in the aggregate. This is supported also by larger rotational hydrodynamic radii measured on cholesterol deuterated at positions C2, C3, C4, and C6. This shows that the aggregate formation is driven by the hydrogen-bonding between cholesterol molecules. 相似文献
469.
Nakahara H Nakamura S Nakamura K Inagaki M Aso M Higuchi R Shibata O 《Colloids and surfaces. B, Biointerfaces》2005,42(2):157-174
The surface pressure (pi)-area (A), the surface potential (DeltaV)-A and the dipole moment (mu( perpendicular))-A isotherms were obtained for two-component monolayers of two different cerebrosides (LMC-1 and LMC-2) with phospholipids of dipalmitoylphosphatidylcholine (DPPC) and with dipalmitoylphosphatidylethanolamine (DPPE) on a subphase of 0.5 M sodium chloride solution as a function of phospholipid compositions by employing the Langmuir method, the ionizing electrode method, and the fluorescence microscopy. Surface potentials (DeltaV) of pure components were analyzed using the three-layer model proposed by Demchak and Fort. The contributions of the hydrophilic saccharide group and the head group to the vertical component of the dipole moment (mu( perpendicular)) were estimated. The miscibility of cerebroside and phospholipid in the two-component monolayers was examined by plotting the variation of the molecular area and the surface potential as a function of the phospholipid molar fraction (X(phospholipid)), using the additivity rule. From the A-X(phospholipid) and DeltaV(m)-X(phospholipid) plots, partial molecular surface area (PMA) and apparent partial molecular surface potential (APSP) were determined at the discrete surface pressure. The PMA and APSP with the mole fraction were extensively discussed for the miscible system. Judging from the two-dimensional phase diagrams, these can be classified into two types. The first is a positive azeotropic type; the combinations of cerebrosides with DPPC are miscible with each other. The second is a completely immiscible type: the combination of cerebrosides with DPPE. Furthermore, a regular surface mixture, for which the Joos equation was used for the analysis of the collapse pressure of two-component monolayers, allowed calculation of the interaction parameter (xi) and the interaction energy (-Delta epsilon) between the cerebrosides and DPPC component. The miscibility of cerebroside and phospholipid components in the monolayer state was also supported by fluorescence microscopy. 相似文献
470.
Matsumoto Y Nakahara H Moroi Y Shibata O 《Langmuir : the ACS journal of surfaces and colloids》2007,23(19):9629-9640
The novel perfluorinated double long-chain salts with divalent counterions of separate electric charge, 1,1-(1,omega-alkanediyl)-bispyridinium perfluorotetradecane- carboxylate [CnBP(FC14)2 : n = 2, 6, 10, 14], were newly synthesized and their interfacial behavior was investigated by Langmuir monolayer methods. Surface properties [surface pressure (pi)-, surface potential (DeltaV)-, dipole moment (micro perpendicular)-area (A) isotherms] and morphological images of CnBP(FC14)2 monolayers on a subphase of water and on various NaCl concentrations were measured by employing the Wilhelmy method, the ionizing electrode method, fluorescence microscopy (FM), and Brewster angle microscopy (BAM). CnBP(FC14)2 formed a stable monolayer on water at 298.2 K, where these pi-A isotherms shifted to a larger molecular area with increasing charge separation and had no transition point from a disordered phase to an ordered one. On the contrary, the pi-A isotherms on NaCl solutions moved to the smaller areas, showed the transition and higher collapse pressures compared to the pi-A isotherms on water. These results suggested that a sodium chloride subphase induced the condensation of CnBP(FC14)2 molecules upon compression. In addition, it is quite noticeable that a dissociation of CnBP counterion from CnBP(FC14)2 occurs on NaCl solutions, depending on the extent of charge separation. This phenomenon was supported by the changes of the limiting area, transition pressure, collapse pressure, repeated compression-expansion cycle curve, and DeltaV behavior of perfluorotetradecanoic acid (FC14). Furthermore, temperature dependence of these monolayers was investigated, and an apparent molar quantity change on the phase transition was evaluated on 0.15 M NaCl. The morphological behavior of CnBP(FC14)2 and FC14 monolayers was also confirmed by FM and BAM images. 相似文献