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11.
Denise Baudry Michel Ephritikhine Hugh Felkin Yves Dromzee Yves Jeannin 《Journal of organometallic chemistry》1984,272(3):403-409
Bis(triphenylphosphine)(η-cyclohexa-1,3-diene)rhenium trihydride, (Ph3P)2(η-C6H8)ReH3 (I) crystallises in the space group C2/c with cell dimensions a 22.76(2), b 10.14(1) c 29.813(6) Å, β 97.69(8)°. The final refinement of 126 variables using 1580 non-zero reflections resulted in a final R value of 0.064. In spite of uncertainties in some of the atomic positions, the structure of I is compatible with a trihydrido diene compound with a distorted pentagonal bipyramidal configuration, rather than with a dihydrido cyclohexenyl compound having an “agostic” CH ? Re interaction. The factors which govern the structure of the complexes (Ph3P)2(η-1,3-diene)ReH3 are discussed. 相似文献
12.
Jocelyn Jalbert Roland Gilbert Pierre Tétreault Brigitte Morin Denise Lessard-Déziel 《Cellulose (London, England)》2007,14(4):295-309
In this study, headspace gas chromatography/mass spectrometry has been used to assess the volatile by-products generated by
the ageing of oil-impregnated paper insulation of power transformers. Sealed-glass ampoules were used to age under oxidative
conditions 0.5-g specimens of insulating paper in 9 mL of inhibited mineral oil in a temperature range of 60–120 °C and moisture
of 0.5, 1 and 2% (w/w). A linear relationship between one of the oil-soluble degradation by-products, i.e. methanol, and the
number of ruptured 1,4-β-glycosidic bonds of cellulose, regardless of the type of paper (ordinary Kraft or thermally-upgraded
(TU) Kraft paper), was established for the first time in this field. Ageing at 130 °C of model compounds of the Kraft paper
constituents (α-cellulose, hemicellulose and lignin) and two cellulosic breakdown by-products (D-(+)-glucose and 1,6-anhydro-β-d-glucopyranose) confirmed that the α-cellulose degradation was mostly responsible for the presence of this molecule in the
system. Furthermore, additional 130 °C-tests with six different papers and pressboard samples under a tight control of initial
moisture indicated that at least one molecule of methanol is formed for each rupture of 1,4-β-glucosidic bond of the molecular
chains. Stability tests showed that the ageing indicator is stable under the oxygen and temperature conditions of open-breathing
transformers. The presence of methanol was detected in 94% of oil samples collected from over than 900 in-service pieces of
equipment, confirming the potential for this application. Lastly, the tests have shown that oil-oxidation by-products and
TU-nitrogenous agents modify the methanol partitioning coefficients in the paper/oil/air system, which makes their study essential
over a range of field conditions encountered by power transformers. Results are presented and discussed in comparison with
2-furfuraldehyde, which is the current reference in the domain. 相似文献
13.
Summary In a series of hexacoordinated nickel(II) complexes, prepared from thio-, sulphinyl, and carbonyl derivatives of pyridine and pyrimidine, the endocyclic N-atom was always the preferred basic site; the sulphinyl O-atom was also a donor centre, forming 5-membered heterocycles, whereas the carbonyl O-atom did not bond to the metal. Alkylthio derivatives did not react, unlike thiolate anions, which form N, S-bonded 4-membered rings. On the other and 2,2-bis(pyridyl)ketone bonded exclusively through the N-atoms, forming 6-membered cycles. 相似文献
14.
The molecular energy of the complex (η5-C5H5)2TiCl2 has been calculated for experimental geometry and for several hypothetical forms by a semi-empirical CNDO/2 approach. The energy difference between experimental (quasi-tetrahedral) geometry and a planar geometry is ca. 20 kcal mol?1. This difference is sufficiently high to explain the difficulty of the inversion process. 相似文献
15.
Multiple oxidants have been implicated as playing a role in cytochrome P450-mediated oxidations. Herein, we report results on N-dealkylation, one of the most facile reactions mediated by P450 enzymes. We have employed the N-oxides of a series of para-substituted 13C2H2-labeled N,N-dimethylanilines to function as both substrates and surrogate oxygen atom donors for P450cam and P4502E1. Kinetic isotope effect profiles obtained using the N-oxide system were found to closely match the profiles produced using the complete NAD(P)H/NAD(P)-P450 reductase/O2 system. The results are consistent with oxidation occurring solely through an iron-oxene species. 相似文献
16.
17.
Christopher Irwin Angelit Barnes Denise Veres Kays Kaidbey 《Photochemistry and photobiology》1993,57(3):504-507
The wavelength dependence for immediate pigment darkening (IPD) was investigated by exposing the midback skin of volunteers to a series of incremental fluences of narrow waveband radiation isolated by band-pass filters in the310–400 nm region. The threshold IPD fluence for each waveband was determined by visual assessment of the skin responses immediately after each exposure. The action spectrum, constructed from the mean threshold fluences, was broad and extended from 320 nm to 400 nm with a peak at around 340 nm. No IPD could be evoked at 310 nm, even after erythemogenic fluences. The spectrum was similar in each of the three skin types investigated (III, IV, V). The broad nature of the action spectrum within the UVA region suggests that IPD may serve as an alternative endpoint for measuring photoprotection against these wavelengths. 相似文献
18.
19.
Prediction of the glass transition temperature for compatible polymer blends of varying compositions
Compatible polymer blends have been found to have widespread commercial applications. The simplest criterion for judging polymer—polymer miscibility in the solid state is the glass transition temperature (Tg), which can vary widely according to blend composition for a compatible system.Recently, an equation which predicts the Tg of intimate mixtures of compatible polymers has been derived, based on classical thermodynamics. Only a knowledge of the Tg and heat capacity increment (ΔCp) of each pure component is required to predict the Tg at any composition.In this paper, the validity of this entropy-based relationship is investigated for a variety of commercial compatible polymer blends, including some based on poly(vinyl chloride), polystyrene, and poly(2,6-dimethyl-,4-phenylene oxide). The Tg and ΔCp of each pure component are measured with a Perkin-Elmer DSC-2 differential scanning calorimeter, are predicted glass transition temperatures are compared with those observed experimentally. 相似文献
20.
Castro LB Almeida AT Petri DF 《Langmuir : the ACS journal of surfaces and colloids》2004,20(18):7610-7615
Hydrophobic films of polystyrene synthesized in bulk (PS) and by emulsion polymerization in the presence of the cationic surfactant cetyltrimethylammonium bromide (PS-CTAB) or the anionic surfactant sodium dodecyl sulfate (PS-SDS) were characterized by means of ellipsometry, contact angle measurements, and atomic force microscopy. Thin (approximately 65 nm) and thick (approximately 300 nm) films were spin-coated on hydrophilic silicon wafers. PS films presented scarcely tiny holes, while PS-CTAB and PS-SDS films presented holes and protuberances. The former were attributed to dewetting effects and the latter to surfactant clusters. The films were exposed to water or to a 0.1 mol/L NaCl solution for 24 h. Ex situ measurements evidenced strong topographic alterations after the exposure to the fluid. A model based on the diffusion of water (or electrolyte) molecules to the polymer/silcon dioxide interface through holes or defects on the film edges was proposed to explain the appearance of wrinkles and protuberances. In situ ellipsometric measurements were performed and compared with simulations, which considered either a water layer between a polymer and a silcon dioxide layer or an air layer between a polymer and water (medium). In the case of thin PS films, the ellipsometric angles evidenced a very thin (0.5-1.0 nm) air layer between water and the PS films. Upon increasing the PS film thickness, no air layer could be observed by ellipsometry. Regardless of the thickness, the ellipsometric data obtained for PS-CTAB and PS-SDS films did not indicate the presence of an air layer between them and the aqueous media. The dramatic changes in the topography of PS, PS-CTAB, and PS-SDS after immersion in salt solution were explained with proposed models. From a practical point of view, this study is particularly relevant because many hydrophobic polymers are used as substrates for biomedical purposes, where the physiological ionic strength is 0.15 mol/L NaCl. 相似文献