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61.
Kittaka S Iwashita T Serizawa A Kranishi M Takahara S Kuroda Y Mori T Yamaguchi T 《The journal of physical chemistry. B》2005,109(49):23162-23169
The effect of confinement on the phase changes and dynamics of acetonitrile in mesoporous MCM-41 was studied by use of adsorption, FT-IR, DSC, and quasi-elastic neutron scattering (QENS) measurements. Acetonitrile molecules in a monolayer interact strongly with surface hydroxyls to be registered and perturb the triple bond in the C[triple bond]N group. Adsorbed molecules above the monolayer through to the central part of the cylindrical pores are capillary condensed molecules (cc-acetonitrile), but they do not show the hysteresis loop in adsorption-desorption isotherms, i.e., second order capillary condensation. FT-IR measurements indicated that the condensed phase is very similar to the bulk liquid. The cc-acetonitrile freezes at temperatures that depend on the pore size of the MCM-41 down to 29.1 A (C14), below which it is not frozen. In addition, phase changes between alpha-type and beta-type acetonitriles were observed below the melting points. Application of the Gibbs-Thomson equation, assuming the unfrozen layer thickness to be 0.7 nm, gave the interface free energy differences between the interfaces, i.e., Deltagamma(l/alpha) = 22.4 mJ m(-2) for the liquid/pore surface (ps) and alpha-type/ps, and Deltagamma(alpha/beta) = 3.17 mJ m(-2) for alpha-type/ps and beta-type/ps, respectively. QENS experiments substantiate the differing behaviors of monolayer acetonitrile and cc-acetonitrile. The monolayer acetonitrile molecules are anchored so as not to translate. The two Lorentzian analysis of QENS spectra for cc-acetonitriles showed translational motion but markedly slowed. However, the activation energy for cc-acetonitrile in MCM-41 (C18) is 7.0 kJ mol(-1) compared to the bulk value of 12.7 kJ mol(-1). The relaxation times for tumbling rotational diffusion of cc-acetonitrile are similar to bulk values. 相似文献
62.
Fukuyama Y Minami H Matsuo A Kitamura K Akizuki M Kubo M Kodama M 《Chemical & pharmaceutical bulletin》2002,50(3):368-371
New five seven-membered vibsane-type diterpenes named 5-epi-vibsanin C, 5-epi-vibsanin H, 5-epi-vibsanin K, 18-O-methyl-5-epi-vibsanin K and 5-epi-vibsanin E have been isolated from the leaves of Viburnum awabuki (Caplifoliaceae). Their structures have been elucidated by analyses of spectroscopic data and comparison of their spectral data with those of the previously known seven-membered vibsane-type diterpenes. The occurrence of these seven-membered vibsane-type diterpenes with a cis relationship on the C-5 and C-10 positions in nature have been predicted by conformational analysis of vibsanin B, an eleven-membered vibsane-type diterpene. Vibsanin C, 5-epi-vibsanin C and 5-epi-vibsanin H exhibited moderate cytotoxic activities on KB cells. 相似文献
63.
Sun Y Irie M Kishikawa N Wada M Kuroda N Nakashima K 《Biomedical chromatography : BMC》2004,18(8):501-507
A highly sensitive HPLC method was developed for the determination of xenoestrogenic compound, bisphenol A (BPA) in human breast milk samples. After a two-step liquid-liquid extraction, BPA was derivatized with fluorescent labeling reagent, 4-(4,5-diphenyl-1H-imidazol-2-yl)benzoyl chloride (DIB-Cl). The excess fluorescent reagent could be removed effectively using a column-switching system. The separation of DIB-BPA from endogenous materials in milk was carried out on two C(18) columns and fluorescence intensity was monitored at 475 nm with the excitation of 350 nm. A good linearity (r = 0.994) was observed of BPA in the concentration range of 0.2-5.0 ng mL(-1) in breast milk, and the detection limit was 0.11 ng mL(-1) at a signal-to-noise ratio of 3. Intra- and inter-day precision (RSD, %) were less than 8.7 and 10.4, respectively. Twenty-three breast milk samples of healthy lactating women were analyzed for the BPA concentration; the mean value was 0.61 +/- 0.20 ng mL(-1), with no correlation to the lipid content of milk samples. 相似文献
64.
P. K. Kuroda I. O. Essien Deig-nevy Sandoval 《Journal of Radioanalytical and Nuclear Chemistry》1984,84(1):23-32
A marked increase in the concentration of238U in rain was observed at Fayetteville (36 °N, 94 °W), Arkansas, after the 18 May 1980 eruption of Mount St. Helens. The fallout of natural uranium observed during the summer months of 1980 can be attributed to the 18 May 1980 events, which ejected an amount of ash material on the order of 4 km3 or about 8·1015 grams into the atmosphere.234U and235U were found to be highly enriched relative to238U in several rain samples collected at Fayetteville, Arkansas, prior to the volcanic eruption. The anomalous uranium seems to have originated from the Soviet satellite Cosmos-954, which fell over Canada, on 24 January 1978. The effect of the 25th Chinese nuclear test, which occurred on 16 October 1980, on the concentrations of uranium isotopes in rain appears to have been insignificant. 相似文献
65.
Shigeo Minami 《Mikrochimica acta》1987,93(1-6):309-324
Multichannel Fourier transform spectrometers utilizing image sensing devices are reviewed along with the instrumental design concepts. Although the idea itself is fairly simple, a photographic plate in holographic spectroscopy is replaced by an image sensor, there are stringent requirements to be satisfied in order to realize the system for field use. Mainly two types of the instrument, which are characterized by the Sagnac common-path interferometer and the polarization interferometer optics, respectively, are described with regard to their system performances. Examples of the system operation introduced show that Fourier transform spectrometers without mechanical moving parts play an important role in a variety of spectroscopic applications under severe surroundings. In a summary, methods for the resolution enhancement and comments on the signal-to-noise ratio are also included. 相似文献
66.
S. Salaymeh S. C. Lee P. K. Kuroda 《Journal of Radioanalytical and Nuclear Chemistry》1987,111(1):147-155
Radiochemical measurements of239,240Pu were carried out for a total of 57 individual rain and snow samples collected at Fayetteville (36 °N, 94 °W), Arkansas, during the period between November 1984 and June 1986. The results indicate that the fallout of plutonium observed during the past three years is due, primarily, to the nuclear debris originating from the 7 February 1983 burn-up of the nuclear-powered Soviet satellite Cosmos-1402.This investigation was supported by the National Science Foundation under Grant ATM 84-07618. 相似文献
67.
P. K. Kuroda T. Barbod S. N. Bakhtiar 《Journal of Radioanalytical and Nuclear Chemistry》1987,111(1):137-146
Marked variations in the ratios of228Th/232Th,230Th/232Th and238U/232Th ratios were observed in rain samples collected at Fayetteville (36°N, 94°W), Arkansas, during 1980 through 1983. These variations are attributed to the fallout from the 1980 and 1982 eruptions of Mount St. Helens and El Chichón volcanoes.This investigation was supported by the National Science Foundation under Grant ATM 84-07618. 相似文献
68.
Principles of the thorium-230 dating method were applied to the study of thorium and uranium isotopes in a series of rain samples collected at Fayetteville (36°N, 94°W), Arkansas, since 1980. The results indicate that the rainwater contains volcanic ash materials with a wide variety of ages, which were blown up onto the upper stratosphere from the 18 May 1980 eruption of Mount St. Helens and the 28 March 1982 eruption of E1 Chichón. These volcanic materials seem to have stayed airborne for a number of years and profoundly affected the global atmospheric inventories of thorium and uranium isotopes.This investigation was supported by the National Science Foundation under Grant ATM 84-07618. 相似文献
69.
A combined anion-exchange-spectrophotometric method has been developed for the determination of vanadium in silicate rocks. A rock sample weighing about 0.1 g is decomposed with a mixture of sulphuric and hydrofluoric acids and after removal of HF the residue is taken up with dilute sulphuric acid. This solution is adjusted to be 0.05M in sulphuric acid and contain 0.3% hydrogen peroxide, and is passed through a column of Amberlite CG 400 (sulphate form). The sorbed vanadium is eluted with 30 ml of 1M hydrochloric acid. The effluent is evaporated to dryness, made 0.1M in hydrochloric acid and 3% in hydrogen peroxide content, and passed through a column of Amberlite CG 400 (chloride form) to get rid of accompanying thorium and zirconium. Vanadium is stripped by elution with 20 ml of 1M hydrochloric acid and subsequently determined spectrophotometrically with 4-(2-pyridylazo)resorcinol. The detection limit is 0.4 ppm. 相似文献
70.
A simple and sensitive method is described for the determination of biogenic indole compounds adsorbed on cellulose or alumina plates for thin-layer chromatography by room-temperature phosphorimetry. The optimum conditions were investigated for 5-hydroxyindole-3-acetic acid and indole-3-acetic acid. The compounds are spotted on the plates, which are then sprayed successively with sodium citrate or sodium acetate, and sodiu iodide solutions. The plates are dried completely under a stream of dry nitrogen, and immediately dipped in molten paraffin. The phosphorescence is stable for at least 3 h even in moist air. The limits of detection for nine biogenic indole compounds tested are between 2 and 300 pmol per sample spot. 相似文献