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91.
Imdad Ullah Mohammadzai Tomoko Ashiuchi Satoshi Tsukahara Yasuaki Okamoto Terufumi Fujiwara 《中国化学会会志》2005,52(5):1037-1042
A simple and fast flow method for the trace level determination of p‐toluidine, 2‐methyl‐5‐nitroaniline, and 2,4‐dinitroaniline in aqueous samples is reported. These amino/nitroaromatics are related to trinitrotoluene (TNT) and appear during the degradation process of the explosive. The chemical principles of ion‐pair formation and liquid‐liquid extraction are applied: In aqueous acidic medium, the protonated analyte [HA]+ makes an ion‐pair with the tetrachloroaurate(III) ion, followed by on‐line ion‐pair extraction into the dichloromethane carrier used. After membrane separation, the CH2Cl2 containing the ion‐pair, [HA]+[AuCl4]−, is mixed with the reversed micellar luminescent reagent of luminol (in 0.3 M Na2CO3) prepared from cetyl‐trimethylammonium chloride in CH2Cl2‐cyclohexane and the [AuCl4−‐luminol chemiluminescence (CL) output is recorded. The detection limits (S/N> 3) are: p‐toluidine, 1.0 × 10−4M; 2‐methyl‐5‐nitroaniline, 1.0 × 10−7 M; 2,4‐dinitroaniline, 1.0 × 10−7 M, while the calibration curves are linear between 1.0 × 10−4 — 1.0 × 10−2 M for all the compounds. Although spectral studies indicated the formation and extraction of a very small amount of the ion‐pair species, the reversed micellar‐mediated CL detection system provides an alternative procedure for the determination of degradation products of the explosive TNT in environmental aqueous samples. 相似文献
92.
Coherent spectroscopy of semiconductor quantum dots, such as photon echo, accumulated photon echo, interferometric coherency measurement, quantum beat and coherent phonon measurement, are reviewed in relation to the historical progress in the coherent spectroscopy of semiconductors. 相似文献
93.
This study describes the framework of the quantum mechanical (QM)/Monte Carlo (MC)/free‐energy perturbation (FEP) method, a FEP method based on MC simulations using quantum chemical calculations. Because a series of structures generated by interpolating internal coordinates between transition state and reactant did not produce smooth free‐energy profiles, we used structures from the intrinsic reaction coordinate calculations. This method was first applied to the Diels–Alder reaction between methyl vinyl ketone and cyclopentadiene and produced ΔG values of 20.1 and 21.4 kcal mol?1 in aqueous and methanol solutions, respectively. They are very consistent with the experimentally observed values. The other two applications were the free‐energy surfaces for the Cope elimination of N,N‐dimethyl‐3‐phenylbutan‐2‐amine oxide in aqueous, dimethyl sulfoxide, and tetrahydrofuran solutions, and the Kemp decarboxylation of 6‐hydroxybenzo‐isoxazole‐3‐carboxylic acid in aqueous, dimethyl sulfoxide, and CH3CN solutions. The calculated activation free energies differed by less than 1.8 kcal mol?1 from the experimental values for these reactions. Although we used droplet models for the QM/MC/FEP simulations, the calculated results for three reactions are very close to the experimental data. It was confirmed that most of the interactions between the solute and solvents can be described using small numbers of solvent molecules. This is because a few solvent molecules can produce large portions of the solute–solvent interaction energies at the reaction centers. When we confirmed the dependency on the droplet sizes of solvents, the QM/MC/FEP for a large droplet with 106 water molecules produced a ΔG value similar to the experimental values, as well as that for a small droplet with 34 molecules. © 2010 Wiley Periodicals, Inc. J Comput Chem, 2011 相似文献
94.
Watanabe M Yamamoto T Yamamoto A Obana E Niiyama K Hada T Ooie T Kataoka M Hori T Houchi H Shinohara Y 《Applied biochemistry and biotechnology》2011,165(2):538-547
The thermogenic function of brown adipose tissue (BAT) is known to be markedly elevated when animals are exposed to the cold, and intensive studies have been carried out to understand the molecular basis enabling effective thermogenesis in cold-exposed animals. In this study, we used microarray analysis to examine the effects of cold exposure of animals on their gene expression profiles in white adipose tissue (WAT), which seems to function as a counterpart tissue of BAT. The results indicate that the effects of cold exposure on the gene expression profiles of WAT were much more moderate than the effects on those of BAT. Possible reasons for the different responses of BAT and WAT to cold exposure are discussed. 相似文献
95.
Matsumoto J Sugiura Y Yuki D Hayasaka T Goto-Inoue N Zaima N Kunii Y Wada A Yang Q Nishiura K Akatsu H Hori A Hashizume Y Yamamoto T Ikemoto K Setou M Niwa S 《Analytical and bioanalytical chemistry》2011,400(7):1933-1943
Schizophrenia is one of the major psychiatric disorders, and lipids have focused on the important roles in this disorder. In fact, lipids related to various functions in the brain. Previous studies have indicated that phospholipids, particularly ones containing polyunsaturated fatty acyl residues, are deficient in postmortem brains from patients with schizophrenia. However, due to the difficulties in handling human postmortem brains, particularly the large size and complex structures of the human brain, there is little agreement regarding the qualitative and quantitative abnormalities of phospholipids in brains from patients with schizophrenia, particularly if corresponding brain regions are not used. In this study, to overcome these problems, we employed matrix-assisted laser desorption/ionization imaging mass spectrometry (IMS), enabling direct microregion analysis of phospholipids in the postmortem brain of a patient with schizophrenia via brain sections prepared on glass slides. With integration of traditional histochemical examination, we could analyze regions of interest in the brain at the micrometric level. We found abnormal phospholipid distributions within internal brain structures, namely, the frontal cortex and occipital cortex. IMS revealed abnormal distributions of phosphatidylcholine molecular species particularly in the cortical layer of frontal cortex region. In addition, the combined use of liquid chromatography/electrospray ionization tandem mass spectrometry strengthened the capability for identification of numerous lipid molecular species. Our results are expected to further elucidate various metabolic processes in the neural system. 相似文献
96.
Akiko Hori Yuta Inoue Hidetaka Yuge 《Acta Crystallographica. Section C, Structural Chemistry》2011,67(5):o154-o156
4‐Chloro‐5‐(2‐phenoxyethoxy)phthalonitrile, C16H11ClN2O2, (I), and 4‐chloro‐5‐[2‐(pentafluorophenoxy)ethoxy]phthalonitrile, C16H6ClF5N2O2, (II), show different types of electrostatic interaction. In (I), the phenoxy and phthalonitrile (benzene‐1,2‐dicarbonitrile) moieties are well separated in an open conformation and intermolecular C—H...π interactions are observed in the crystal packing. On the other hand, in (II), the pentafluorophenoxy moiety interacts closely with the Cl atom to form a folded conformation containing an intramolecular halogen–π interaction. 相似文献
97.
A wetting/dewetting process was utilized to prepare self-organized organic dye particles of micrometer and submicrometer size.
Near-field scanning optical microscopy successfully identified near-field excited near-field fluorescence from single particles.
The majority of the small particles with diameters around 2 mm or less, however, did not show fluorescence under near-field
observation. In contrast, far-field fluorescence, when excited by a polarized evanescent field, was observed, with the intensity
depending on the excitation polarization, indicating that molecules' transition moment within dye particles was oriented parallel
to the substrate surface. Single particle fluorescence spectrum consistently showed an identical sharp peak with a large redshift,
indicating that the particles were composed of identical dye aggregates similar to J-aggregates. These observations suggest
that the near-field at the probe tip was polarized parallel to the probe axis. Another observation, that molecules were oriented
in a similar direction among adjacent particles, suggests that the dewetting process contributed to the alignment of the molecular
direction among adjacent particles, which further proves that the present specimen was formed by a self-organizing mechanism. 相似文献
98.
99.
100.
Perfluorocarboxylic acids and their anions (PFCAs), such as perfluorooctanate (C7F15C(O)O?), have been generally recognized to be global pollutants and are believed to persist in the environment. Kinetic data for reactions of sulfate anion radicals (SO4?) with PFCAs are needed to evaluate the residence times of PFCAs in the environment, but no kinetic data have been reported, except for the rate constant for the reaction of SO4? with trifluoroacetate (CF3C(O)O?) (k1). In this study, using the fact that PFCAs react with SO4? to form shorter chain PFCAs, we determined rates relative to k1 of the reactions of photolytically generated SO4? with two short‐chain PFCAs, pentafluoropropionate (C2F5C(O)O?; k2) and heptafluorobutyrate (C3F7C(O)O?; k3), along with conversion ratios for conversion of C2F5C(O)O? into CF3C(O)O? (α) and conversion of C3F7C(O)O? into C2F5C(O)O? (β) and CF3C(O)O? (γ) at 298 K. Values of k1, k2, or k3 might change over the course of reaction with increasing ionic strength. Nevertheless, if the values of k1/k2, k2/k3, α, β, and γ remain almost constant during the reaction, a simple equation involving relative rates, such as k1/k2, can be used to relate the concentrations of C3F7C(O)O?, C2F5C(O)O?, and CF3C(O)O?. We compared the relative rates, such as k1/k2, and the conversion ratios determined from various experimental runs with different initial conditions to check whether relative rates and conversion ratios remained almost constant during each experimental run. The values of k1/k2, k2/k3, α, β, and γ seemed to remain almost constant, which facilitated determination of k2/k1 = 0.89 ± 0.07, k3/k1 = 0.84 ± 0.08, α = 0.88 ± 0.05, β = 0.75 ± 0.05, and γ = 0.17 ± 0.02. © 2007 Wiley Periodicals, Inc. Int J Chem Kinet 39: 276–288, 2007 相似文献