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91.
Gutiérrez-Dabán A Fernández-Espinosa AJ Ternero-Rodríguez M Fernández-Alvarez F 《Analytical and bioanalytical chemistry》2005,381(3):721-736
The size distribution of polycyclic aromatic hydrocarbons (PAH) was determined for airborne particles from a large city with high vehicular traffic. The analytical method was optimised and validated using NIST standard reference material (SRM 1649a Urban Dust). The 16 priority PAH listed in the US-EPA were Soxhlet-extracted from filtered particulate matter and then fractionated using on-column chromatography. The aromatic fraction was quantified by gas chromatography-mass spectrometry. Real samples of particles collected in Seville (Spain) were analysed using the validated method. Values for the total concentration of PAH in the air, as well as the concentrations of each PAH in six particle-size ranges were obtained. Values of the PAH in TSP, PM10, PM2.5 and PM1 were assessed. 相似文献
92.
Richard D. Chambers Julian F. S. Vaughan Steven J. Mullins 《Research on Chemical Intermediates》1996,22(8):703-715
t-Butylhydroperoxide/butyl-lithium is a good reagent for synthesis of epoxides and diepoxides from polyfluorinated-alkenes and-polyenes. This reagent and calcium hypochlorite both give a novel diepoxide 5 from perfluoro-3,4-dimethyl-2,4-diene 1; diepoxide 5 undergoes a novel rearrangement, at 200°C, to the corresponding 1,4-dioxine derivative 18. Possible mechanisms are discussed. 相似文献
93.
Antonio Fernández-Ramos Benjamin A. Ellingson Rubén Meana-Pañeda Jorge M. C. Marques Donald G. Truhlar 《Theoretical chemistry accounts》2007,118(4):813-826
This article shows how to evaluate rotational symmetry numbers for different molecular configurations and how to apply them
to transition state theory. In general, the symmetry number is given by the ratio of the reactant and transition state rotational
symmetry numbers. However, special care is advised in the evaluation of symmetry numbers in the following situations: (i)
if the reaction is symmetric, (ii) if reactants and/or transition states are chiral, (iii) if the reaction has multiple conformers
for reactants and/or transition states and, (iv) if there is an internal rotation of part of the molecular system. All these
four situations are treated systematically and analyzed in detail in the present article. We also include a large number of
examples to clarify some complicated situations, and in the last section we discuss an example involving an achiral diasteroisomer. 相似文献
94.
Julian Tyson 《Trends in analytical chemistry : TRAC》1985,4(7):IV-V
Professional scientific societies are becoming increasingly aware of the public image of their members' activities. The Analytical Division of the Royal Society of Chemistry, through the activities of its Honorary Publicity Secretary, is making a conscious effort to inform young people about the activities of analytical chemists and to interest them in the profession of analytical chemistry. 相似文献
95.
E. Fernández-Sánchez A. Fernández-Torres J. A. García-Domínguez J. M. Santiuste 《Chromatographia》1991,31(1-2):75-79
Summary A correlation between the retention polarity and the Kováts' coefficient has been found for a number of commercial stationary phases used in gas chromatography. The correlation has been used to predict the polarity of a few mixed stationary phase columns prepared as binary mixtures of OV-101 with OV-25, DC-550 or Carbowax 20M, and also mixtures of OV-225 with SP-2340. A linear relationship was found between polarity and mixture composition. The temperature dependence of the Kováts' coefficient was investigated and found to increase linearly with temperature, the rate of increase depending on the polarity of the stationary phase, with greater increases for more polar stationary phases. 相似文献
96.
97.
M. T. Fernández-Díaz J. Rodríguez-Carvajal J. L. Martínez G. Fillion F. Fernández R. Saez-Puche 《Zeitschrift für Physik B Condensed Matter》1991,82(2):275-282
Neutron powder diffraction and magnetization measurements have been performed in stoichiometric Pr2NiO4+(0), which at room temperature (RT) is orthorhombic (Bmab). Ni2+ becomes three dimensionally (3D) antiferromagnetically ordered atT
N
325K, with a propagation vectork=[100], and spins oriented along thea axis (parallel to the propagation vector). The magnetic structure belongs to the
7g
(––+)-representation (g
x
mode, Shubnikov groupB
pmab') ofBmab, and a magnetic moment of 1.5
B
is measured at 155K. This compound undergoes two different structural phase transitions. First, going down in temperature, Pr2NiO4 transforms by a first order phase transition from orthorhombic (Bmab) to tetragonal (P42/ncm) atT
c1115K. At high temperature, we can predict a transformation from orthorhombic (Bmab) to tetragonal (I4/mmm) in a continuous way. The extrapolated temperature for this second structural transition isT
c21500±100K. The low temperature structural transformation allows a change in the magnetic structure which forT<T
c1 is better described in the orthorhombic symmetry. Just belowT
c1 the magnetic structure is described by the:
3g
(–+)-representation ofPccn(gxcyfz mode, Shubnikov groupPccn), this magnetic phase begins to disappear going down in temperature and at the same time a new magnetic phase grows. This new magnetic structure is described by the
1g
ofPccn (c
xgyaz mode, Shubnikov groupPccn). Both magnetic structures coexist in a certain temperature range. At 1.5 K thec
xgyaz mode represents the total of the magnetic ordering. To reproduce the observed magnetic intensities we are forced to consider that Pr3+ is polarized below 40 K, with a magnetic structure which is coupled to the Ni sublattices (i.e.
1g
and
3g
). The magnetic moment at low temperature for Pr is about 1.28
B
. 相似文献
98.
99.
Kocher N Henn J Gostevskii B Kost D Kalikhman I Engels B Stalke D 《Journal of the American Chemical Society》2004,126(17):5563-5568
The concept of hypervalency in molecules, which hold more than eight valence electrons at the central atom, still is a topic of constant debate. There is general interest in silicon compounds with more than four substituents at the central silicon atom. The dispute, whether this silicon is hypervalent or highly coordinated, is enlightened by the first experimental charge density determination and subsequent topological analysis of three different highly polar Si-E (E = N, O, F) bonds in a hexacoordinated compound. The experiment reveals predominantly ionic bonding and much less covalent contribution than commonly anticipated. For comparison gas-phase ab initio calculations were performed on this compound. The results of the theoretical calculations underline the findings of the experiment. 相似文献
100.
Chromatographic speciation of anionic and neutral selenium compounds in Se-accumulating Brassica juncea (Indian mustard) and in selenized yeast 总被引:1,自引:0,他引:1
Selenium-accumulating plants such as Brassica juncea (Indian mustard) concentrate the element in plant shoots and roots. Such behavior may provide a cost-effective technology to clean up contaminated soils and waters that pose major environmental and human health problems (phytoremediation). Such ability to transform selenium into bioactive compounds has important implications for human nutrition and health. Element selective characterization of B. juncea grown in the presence of inorganic selenium under hydroponic conditions provides valuable information to better understand selenium metabolism in plants. The present work determines both previously observed organoselenium species such as selenomethionine and Se-methylselenocysteine and for the first time detects the newly characterized S-(methylseleno)cysteine in plant shoots and roots when grown in the presence of selenate or selenite as the only selenium source. A key feature of this study is the complementary role of selenium and sulfur specific chromatographic detection by HPLC with interfaced inductively coupled plasma mass spectrometry (ICP-MS) detection and by derivatization GC with interfaced atomic spectral emission. HPLC-ICP-MS limits of detection for such species were in the range 5-50 ng Se mL(-1) in the injected extracts. Speciation profiles are compared with those of selenium-enriched yeast by both HPLC-ICP-MS and GC-AED. 相似文献