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71.
The nu(C=O) Raman band frequencies of acetone have been analyzed to separate the contributions of the environmental effect and the vibrational coupling to the gas-to-liquid frequency shifts of this band and to elucidate the changes in these two contributions upon dilution in DMSO. We have measured the frequencies of the nu((12)C=O) band in acetone/DMSO binary mixtures, the nu((13)C=O) band of the acetone-(13)C=O present as a natural abundance isotopic impurity in these mixtures, and both the nu((12)C=O) and nu((13)C=O) bands in the acetone-(12)C=O/acetone-(13)C=O isotopic mixtures at infinite dilution. These frequencies are compared with those of the nu((12)C=O) band in the acetone/CCl(4) binary mixtures measured previously. We have found the following three points: (i) The negative environmental contribution for the nu((12)C=O) oscillator of acetone completely surrounded by DMSO is reduced in magnitude by +5.5 cm(-1) and +7.8 cm(-1) upon the complete substitution of DMSO with acetone and CCl(4) molecules, respectively, indicating the progressive reduction of the attractive forces exerted by the environment on the nu((12)C=O) mode of acetone. (ii) In DMSO and other solvents, the contribution of the vibrational coupling to the frequency of the isotropic Raman nu((12)C=O) band of acetone becomes progressively more negative with increasing acetone concentration up to a value of -5.5 cm(-1), while the contribution to the frequency of the anisotropic Raman band remains approximately unchanged. The only difference resides in the curvatures of the concentration dependencies of these contributions which depend on the relative solute/solvent polarity. (iii) The noncoincidence effect (separation between the anisotropic and isotropic Raman band frequencies) of the nu(C=O) mode in the acetone/DMSO mixtures exhibits a downward (concave) curvature, in contrast to that in the acetone/CCl(4) mixtures, which shows an upward (convex) curvature. This result is supported by MD simulations and by theoretical predictions and is interpreted as arising from the reduction and enhancement of the short-range orientational order of acetone in the acetone/DMSO and acetone/CCl(4) mixtures, respectively. 相似文献
72.
Spatial distributions of photothermal refractive index changes in dye-doped liquid crystals were determined by an optical interferometric method. The refractive index change of the order of 10-1, including spatial distribution, was estimated by the described experimental technique. The absolute value of the refractive index change was proportional to the pump beam power, and the diameter of the index distribution was slightly larger than that of the pump laser beam due to heat conduction. 相似文献
73.
The HO2 uptake coefficients (γ) for organic submicron aerosol particles were measured using an aerosol flow tube coupled with a chemical conversion/laser‐induced fluorescence technique under ambient conditions (760 Torr and 296 ± 2 K) and different values of relative humidity (RH) (28% and 68%). Determined uptake coefficients for succinic, glutaric, adipic, and pimelic acid aerosol particles at 28% RH were 0.07 ± 0.02, 0.07 ± 0.03, 0.02 ± 0.01, and 0.06 ± 0.03, respectively, whereas the γ values for those particles at 68% RH were 0.18 ± 0.07, 0.15 ± 0.04, 0.06 ± 0.01, and 0.13 ± 0.04, respectively. An increase in γ with increasing RH was observed for all the dicarboxylic acids, suggesting a contribution by water amount in the particle, aqueous phase chemistry, and uptake of HO2–H2O. The anomalously low γ values for adipic acid are likely related to its high crystallization RH and thus provide a new clue that the water amount and/or RH have a significant influence on HO2 uptake. 相似文献
74.
Uric acid quantification in fingernail of gout patients and healthy volunteers using HPLC‐UV 下载免费PDF全文
Wenlong Jin Gao Li Kenichiro Todoroki Hajime Mizuno Toshimasa Toyo'oka Jun Zhe Min 《Biomedical chromatography : BMC》2016,30(8):1338-1342
The presence of elevated uric acid (UA) levels is a sign of gout, that is, hyperuricemia. In this study the monitoring of the UA levels in less‐invasive biological samples, such as the human fingernail, is suggested for the diagnosis and therapy of gout. Twenty‐six healthy volunteers (HV) and 22 gout patients (GP) were studied. The UA was extracted from human fingernail samples, then separated on an Inertsil ODS‐3 column (250 × 4.6 mm i.d., 4.0 μm, GL Sciences) by isocratic elution using methanol–74 mm phosphate buffer (pH 2.2) 2:98 (v/v). A UV detector was used to monitor the samples at 284 nm. Using the developed method, different UA concentrations were found in the GP and HV. When comparing the concentrations from GP with those from HV, a statistically significant correlation was observed between the UA (p < 0.01). In this study, the UA was confirmed as a potential biomarker for the diagnosis and therapy of gout. We have developed a novel sensitive, and simple method for the determination of UA in the fingernails of GP and HV. The human fingernail may serve as a noninvasive biosample for the diagnosis of gout. Copyright © 2016 John Wiley & Sons, Ltd. 相似文献
75.
76.
Mehrdad Nikravech Kamal Baba Bernard Leneindre Frédéric Rousseau 《Chemical Papers》2012,66(5):502-510
Processing the aerosol of metal salts in non-equilibrium plasma represents a promising technique that combines the advantages
of spray pyrolysis with the high reactivity of plasmas at nearlaboratory temperature in order to produce mixed-oxides and
perovskite materials. The aim of this paper is to describe the principles of this new technique and to present the various
applications and latest developments. This technique’s capacity to deposit various mixed metal oxides with precise stoichiometry
is demonstrated. It is shown that oxidant plasma species play a key role in the chemical transformation of starting materials
into oxides at laboratory temperature, while the configuration of the reactor determines the morphology and texture of the
deposited layers. Two different reactor configurations are presented. The porous layers of La
x
Sr1−x
MnO3 as the cathode for fuel cells were synthesised in a wave shock reactor configuration, while nanostructured ZnO-Al layers
to form a transparent conductive cathode for photovoltaic cells were deposited in the spray plasma reactor of the latest generation
for this technique. The experimental results emphasise the role of plasma species in the rate of chemical reactions and in
the chemical composition of the deposited layers. 相似文献
77.
Enantioselective Sulfoxidation Catalyzed by a Bisguanidinium Diphosphatobisperoxotungstate Ion Pair 下载免费PDF全文
Xinyi Ye Adhitya Mangala Putra Moeljadi Kek Foo Chin Prof. Dr. Hajime Hirao Dr. Lili Zong Prof. Dr. Choon‐Hong Tan 《Angewandte Chemie (International ed. in English)》2016,55(25):7101-7105
The first enantioselective tungstate‐catalyzed oxidation reaction is presented. High enantioselectivities were achieved for a variety of drug‐like phenyl and heterocyclic sulfides under mild conditions with H2O2, a cheap and environmentally friendly oxidant. Synthetic utility was demonstrated through the preparation of (S)‐Lansoprazole, a commercial proton‐pump inhibitor. The active ion‐pair catalyst was identified to be bisguanidinium diphosphatobisperoxotungstate using Raman spectroscopy and computational studies. 相似文献
78.
Extremely Photostable Electron-Deficient Phthalocyanines that Generate High Levels of Singlet Oxygen
Prof. Dr. Taniyuki Furuyama Yusuke Miyaji Kazuya Maeda Prof. Dr. Hajime Maeda Prof. Dr. Masahito Segi 《Chemistry (Weinheim an der Bergstrasse, Germany)》2019,25(7):1678-1682
A robust lead-mediated synthetic procedure for the generation of phthalocyanines substituted with electron-withdrawing groups has been developed. The free-base phthalocyanine and various metal complexes were prepared without discernible degradation of the peripheral electron-withdrawing substituents. Upon irradiation with red light, some of the thus-obtained metal complexes generated high levels of singlet oxygen. In particular, a palladium complex exhibited attractive photostability upon exposure to singlet oxygen as a bleaching agent. The photostability of such complexes that may manifest concomitantly to the generation of high levels of singlet oxygen was attributed to the presence of the electron-withdrawing groups, which results in energetically low-lying highest occupied molecular orbitals. 相似文献
79.
Prof. Jun Ishihara Fuma Usui Tomohiro Kurose Tomohiro Baba Yasunori Kawaguchi Yuki Watanabe Prof. Susumi Hatakeyama 《Chemistry (Weinheim an der Bergstrasse, Germany)》2019,25(6):1543-1552
The upper fragment of spirolides A and B, which are marine phycotoxins that exhibit strong antagonistic activities on nicotinic acetylcholine receptors, was constructed. The functionalized cyclohexene in spirolides was stereoselectively synthesized from the bicyclic lactone, which could be readily accessed by the Lewis acid template-catalyzed asymmetric Diels–Alder reaction of the pentadienol and methyl acrylate. 相似文献
80.
Paulo Limão-Vieira Gustavo García E. Krishnakumar Zoran Petrović James Sullivan Hajime Tanuma 《The European Physical Journal D - Atomic, Molecular, Optical and Plasma Physics》2016,70(10):202
The topical issue on Advances in Positron and Electron Scattering” combines contributionsfrom POSMOL 2015 together with others devoted to celebrate the unprecedented scientificcareers of our loyal colleagues and trusted friends Steve Buckman (Australian NationalUniversity, Australia) and Michael Allan (University of Fribourg, Switzerland) on theoccasion of their retirements. POSMOL 2015, the XVIII International Workshop on Low-EnergyPositron and Positronium Physics and the XIX International Symposium on Electron-MoleculeCollisions and Swarms, was held at Universidade NOVA de Lisboa, Lisboa, Portugal, from17–20 July 2015. The international workshop and symposium allowed to achieve a veryprivileged forum of sharing and developing our scientific expertise on current aspects ofpositron, positronium and antiproton interactions with electrons, atoms, molecules andsolid surfaces, and related topics, as well as electron interactions with molecules inboth gaseous and condensed phases. Particular topics include studies of electroninteractions with biomolecules, electron induced surface chemistry and the study of plasmaprocesses. Recent developments in the study of swarms are also fully addressed. 相似文献