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71.
Many of the interferences reported earlier for the determination of manganese in a graphite furnace were not found when a modern graphite furnace was used. At high levels of chloride matrix, an interference which was observed in the modern furnace was reduced when manganese was determined under constant temperature conditions. In this work, the sample was introduced on a tungsten wire after the graphite furnace had reached a constant, preset temperature. Drying and ashing were accomplished outside the atomization furnace, reducing contamination from matrix materials. 相似文献
72.
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
73.
Ab initio calculations on vinyldifluoroborane yield a -contribution of 23 kJ/mol (5.5 kcal/mol) mainly due to the C=C bond and not to the lone pairs of the fluorine atoms. The rotational barrier was also determined. The force field calculations favour the interpretation of the bond structure derived from the theab initio results. 相似文献
74.
Kumar D Hirao H de Visser SP Zheng J Wang D Thiel W Shaik S 《The journal of physical chemistry. B》2005,109(42):19946-19951
Density functional theory (DFT) is applied to the dark section of the catalytic cycle of the enzyme cytochrome P450, namely, the formation of the active species, Compound I (Cpd I), from the ferric-hydroperoxide species (Cpd 0) by a protonation-assisted mechanism. The chosen 96-atom model includes the key functionalities deduced from experiment: Asp(251), Thr(252), Glu(366), and the water channels that relay the protons. The DFT model calculations show that (a) Cpd I is not formed spontaneously from Cpd 0 by direct protonation, nor is the process very exothermic. The process is virtually thermoneutral and involves a significant barrier such that formation of Cpd I is not facile on this route. (b) Along the protonation pathway, there exists an intermediate, a protonated Cpd 0, which is a potent oxidant since it is a ferric complex of water oxide. Preliminary quantum mechanical/molecular mechanical calculations confirm that Cpd 0 and Cpd I are of similar energy for the chosen model and that protonated Cpd 0 may exist as an unstable intermediate. The paper also addresses the essential role of Thr(252) as a hydrogen-bond acceptor (in accord with mutation studies of the OH group to OMe). 相似文献
75.
Gregory M. Su Han Wang Brandon R. Barnett Jeffrey R. Long David Prendergast Walter S. Drisdell 《Chemical science》2021,12(6):2156
Metal–organic frameworks are promising materials for applications such as gas capture, separation, and storage, due to their ability to selectively adsorb small molecules. The metal–organic framework CuI-MFU-4l, which contains coordinatively unsaturated copper(i) centers, can engage in backbonding interactions with various small molecule guests, motivating the design of frameworks that engage in backbonding and other electronic interactions for highly efficient and selective adsorption. Here, we examine several gases expected to bind to the open copper(i) sites in CuI-MFU-4l via different electronic interactions, including σ-donation, π-backbonding, and formal electron transfer. We show that in situ Cu L-edge near edge X-ray absorption fine structure (NEXAFS) spectroscopy can elucidate π-backbonding by directly probing excitations to unoccupied backbonding orbitals with Cu d-character, even for gases that participate in other dominant interactions, such as ligand-to-metal σ-donation. First-principles calculations based on density functional theory and time-dependent density functional theory additionally reveal the backbonding molecular orbitals associated with these spectroscopic transitions. The energies of the transitions correlate with the energy levels of the isolated small molecule adsorbates, and the transition intensities are proportional to the binding energies of the guest molecules within CuI-MFU-4l. By elucidating the molecular and electronic structure origins of backbonding interactions between electron rich metal centers in metal–organic frameworks and small molecule guests, it is possible to develop guidelines for further molecular-level design of solid-state adsorbents for energy-efficient separations of relevance to industry. In situ near edge X-ray absorption fine structure spectroscopy directly probes unoccupied states associated with backbonding interactions between the open metal site in a metal–organic framework and various small molecule guests. 相似文献
76.
Kinetics of oil saponification by lead salts in ancient preparations of pharmaceutical lead plasters and painting lead mediums 总被引:1,自引:0,他引:1
M. Cotte E. Checroun J. Susini P. Dumas P. Tchoreloff M. Besnard Ph. Walter 《Talanta》2006,70(5):1136
Lead soaps can be found in archaeological cosmetics as well as in oil paintings, as product of interactions of lead salts with oil. In this context, a better understanding of the formation of lead soaps allows a follow-up of the historical evolution of preparation recipes and provides new insights into conservation conditions. First, ancient recipes of both pharmaceutical lead plasters and painting lead mediums, mixtures of oil and lead salts, were reconstructed. The ester saponification by lead salts is determined by the preparation parameters which were quantified by FT-IR spectrometry. In particular, ATR/FT-IR spectrometer was calibrated by the standard addition method to quantitatively follow the kinetics of this reaction. The influence of different parameters such as temperature, presence of water and choice of lead salts was assessed: the saponification is clearly accelerated by water and heating. This analysis provides chemical explanations to the historical evolution of cosmetic and painting preparation recipes. 相似文献
77.
Brunner H Cattey H Meier W Mugnier Y Stückl AC Wachter J Wanninger R Zabel M 《Chemistry (Weinheim an der Bergstrasse, Germany)》2003,9(16):3796-3802
The reaction of the cluster salts [Cp(2*) Nb(CO)(2)](n)[Co(11)Te(7)(CO)(10)] (Cp*=C(5)Me(5); n=1, 2) with excess PMe(2)Ph gave the neutral, dark brown clusters [Co(11)Te(7)(CO)(6)(PMe(2)Ph)(4)] (5) and [Co(11)Te(7)(CO)(5)(PMe(2)Ph)(5)] (6) with 147 metal valence electrons. The new compounds were characterized by IR spectroscopy, elemental analyses, and mass spectrometry. The molecular structure of 6 was determined by X-ray crystallography. Like its precursor anion, it consists of a pentagonal-prismatic [Co(11)Te(7)] core, but with a ligand sphere composed of five CO and five PMe(2)Ph ligands. Detailed electrochemical studies of both reactions reveal that a stepwise substitution of CO ligands in the initial cluster anions takes place leading to intermediate [Co(11)Te(7)(CO)(10-m)(PMe(2)Ph)(m)](n-) ions (m=1-5; n=1, 2). Each of these intermediates is distinguished by at least one oxidation and two reduction waves, giving rise to a total of 21 redox couples and 27 electroactive species. The electron sponge character of the new compounds is particularly pronounced in 5, which exhibits charges n between +1 and -4 corresponding to metal valence electron counts of between 146 and 151. 相似文献
78.
Vlekken J D'Olieslaeger M Knuyt G Vandervorst W De Schepper L 《Journal of the American Society for Mass Spectrometry》2000,11(7):650-658
In secondary ion mass spectrometry, the detection of MCs+ clusters (with M an element of the specimen) under a Cs bombardment is frequently used for the quantification of major elements. Despite some very good results obtained by this method, some problems still remain. In order to gain some more insight into these problems, the formation mechanism of the MCs+ clusters is investigated using a Monte Carlo model. It is shown that the majority of the constituent particles of the formed clusters are initially first or second neighbor atoms at the surface and that the velocity distribution of the MCs+ clusters becomes broader and peaked at higher velocities with increasing surface binding energy of the M atom. In addition, it is demonstrated that the interaction potential between the M and Cs+ particle has no influence on the velocity distribution of the MCs+ clusters. On the other hand, the cluster formation probability, defined as the probability that a sputtered M and Cs+ particle will form a MCs+ cluster, is extremely sensitive to this interaction potential. It is also shown that the cluster formation probability decreases with increasing surface binding energy. Finally, a good correspondence is obtained between the calculated and experimental velocity distributions of MCs+ clusters sputtered from different monoatomic materials. As a consequence, the Monte Carlo model and the discussed results can be validated. 相似文献
79.
Michelle Delayette-Mills Lya Karm Gilbert E. Janauer Ping-Kwan Chan William E. Bernier 《Analytica chimica acta》1981,124(2):365-372
The in situ precipitation of traces of cadmium(II) and zinc(II) ions as hexacyanoferrates from aqueous matrices was studied on conventional polystyrene gel and macroporous cation- and anion-exchange resins. Coprecipitation with each other or with copper(II) ions present in binary cation resins or in solution, and the influence of added nonprecipitating ions of the same charge type such as magnesium(II) were investigated. Microporous (gel) cation exchangers gave reasonable recoveries and macroporous cation exchangers gave very good recoveries; but macroporous anion exchangers performed best, suggesting macroporous hexacyanoferrate(II) resin as an ideal phase for collection/preconcentration of traces of Cu2+, Cd2+, Zn2+, and possibly Co2+, Ni2+, and Pb2+ from waters. As expected, very low yields were obtained with conventional anion exchange resin in the hexacyanoferrate form. Uniform distribution of Cu2+, Zn2+, and Cd2+ over macroporous anion-exchange resin phases were established by means of electron probe scans and taken as evidence for the formation of a uniform, well-developed precipitate layer covering the entire resin particle surface. 相似文献
80.
Walter Purcell Andreas Roodt Stephen S. Basson Johann G. Loipoldt 《Transition Metal Chemistry》1989,14(5):369-370
Summary The light purple crystals of (4,4-dipyridinium) [ReO(NCS)(CN)4] crystallize in the monoclinic space group P21/m witha=6.615(1),b=16.043(1),c=8.405(1) Å,=93.20(1)°,z=2. The anisotropic refinement of the 1770 observed reflections converged to R=0.041.The [ReO(NCS)(CN)4]2– ion has a distorted octahedral geometry. The rhenium atom is displaced by 0.30 Å out of the plane formed by the four carbon atoms towards the terminal oxo ligand. Bond distances: Re=0 =1.67(1), Re–N=2.12(1) and Re–Cav=2.11(1)Å. The thiocyanate ion is nitrogen bonded to the rhenium atom. 相似文献