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991.
Roger N. F. Thorneley 《Journal of organometallic chemistry》1974,70(3):C37-C39
The kinetic isotope effect for β-hydride elimination from alkyliridium(I) complexes has bee found to be kH/kD = 2.28 ± 0.20. 相似文献
992.
Beitz T Kötz J Wolf G Kleinpeter E Friberg SE 《Journal of colloid and interface science》2001,240(2):581-589
The influence of the nonionic polymer poly(N-vinyl-2-pyrrolidone) (PVP) in comparison to the surfactant 1-octyl-2-pyrrolidinone (OP) on the phase behavior of the system SDS/pentanol/xylene/water was studied. In both modified systems a strong increase in the water solubilization capacity was found, accompanied by a change in the spontaneous curvature toward zero. In the polymer-modified system an isotropic phase channel is formed with increasing polymer content that connects the L1 and the L2 phase. The lamellar liquid crystalline phase is destabilized in both cases. In the L1 phase the adsorption of PVP at the surface of the microemulsion droplets and the formation of a cluster-like structure is proven by several methods like 13C NMR T1 relaxation time measurments, zeta potential measurements, and rheology. In the L2 phase a modification of the interface of the inverse droplets is detected by a shift in the percolation boundary (conductivity) and 13C NMR T1 relaxation measurements. The formation of a cluster-like structure can be assumed on the basis of our rheological measurements. 相似文献
993.
Renata Wietecha Paweł Kościelniak Teresa Lech Tomasz Kielar 《Mikrochimica acta》2005,149(1-2):137-144
This study describes a simple, rapid and reliable method for simultaneous determination of selenium and arsenic in human hair by means of atomic fluorescence spectrometry combined with a hydride generation technique (HG-AFS). The procedure developed encompasses microwave digestion of a sample in the nitric acid environment only. The interferences caused by nitrous oxides are eliminated by removing a gas from above the digested solution with a stream of argon. The sample is then chemically treated in a flow-through hydride generation system and exposed to measurements in a double-channel atomic fluorescence spectrometer. The method permits determining both analytes in the linear range of 0.5–100µgL–1 with a detection limit equal to 0.2µgL–1, as well as with very good repeatability not exceeding 1% for Se and 2% for As. No mutual interferences from either of the analytes in the concentrations ranges matching the hair composition were found. The method was verified in terms of accuracy with the use of a reference material and then applied to the analysis of the natural samples of human hair. 相似文献
994.
Bromoacetyl chloride and bromoacetyl bromide are studied by gas phase electron diffraction at nozzle-tip temperatures of 70°C and 77°C, respectively. Both compounds exist as mixtures of anti and gauche conformers. The mole fraction anti, with uncertainties estimated at 2σ, was found to be 0.474(0.080) for bromoacetyl chloride and 0.615(0.069) for bromoacetyl bromide. The results for the distance (ra)and angle (∠α) parameters, with parenthesized uncertainties of 2σ including estimated uncertainty in the electron wave length and correlation effects are as follows: (1) bromoacetyl chloride, r(C-H) = 1.086(0.062) Å, r(CO) = 1.188(0.009) Å, r(C-C) = 1.519(0.018) Å, r(C-Cl) = 1.789(0.011) Å, r(C-Br) = 1.935(0.012) Å, ∠C-CO = 127.6(1.3)°, ∠C-C-Cl = 111.3(1.1)°, ∠C-C-Br = 111.0(1.5)°, ∠H-C-H = 109.5°(assumed), /o (gauche torsion angle relative to 0° for the anti form) = 110.0°(assumed); (2) bromoacetyl bromide, r(C-H) =1.110(0.088) Å, r(C=O) = 1.175(0.013) Å, r(C-C) = 1.513(0.020) Å, r(CO-Br) = 1.987(0.020) Å, r(CH2-Br) = 1.915(0.020) Å, ∠C-CO = 129.4(1.7)°, ∠CH2-CO-Br = 110.7(1.5)°, ∠CO-CH2-Br = 111.7(1.8)°, ∠H-C-H = 109.5°(assumed), ∠ø (gauche torsion angle relative to 0° for the anti form) = 105.0°(assumed). The structural results are discussed in connection with the structures of related molecules. 相似文献
995.
The molecular structure of tetravinylsilane has been studied by gas-phase electron diffraction. The radial distribution curve suggests the absence of conformers having vinyl double bonds staggered with respect to the SiC4 skeleton. Of the eclipsed or approximately-eclipsed conformers, the one with S4 symmetry gives the best fit with experiment, although a small admixture of a C1 conformation cannot be ruled out. Least-squares refinement gave the following values for the independent structural parameters (lengths, ra basis; angles, rα basis): C-H = 1.118 ± 0.003 Å, CC = 1.355 ± 0.002 Å, Si-C = 1.855 ±0.002 Å, ∠SiCC = 124.0 ± 0.3°, ∠SiCH = 118.4 ± 1.0°, torsion angles CSiCC are 17.5 ± 0.6° from the eclipsed conformation. During the refinement the vibrational amplitudes u and perpendicular amplitude corrections K were held constant at calculated values. The CC bond length provides evidence of interaction between the vinyl π-bonds and the vacant d-orbitals of silicon. 相似文献
996.
Thermal- and photo-stabilities of unstabilized acrylonitrile-butadiene-styrene terpolymer, ABS, have been investigated by i.r. spectroscopy. Degradation of ABS samples is initiated by attack on the polybutadiene (PB) component; oxidation products containing hydroxyl and carbonyl groups are produced. The effect of prior thermal processing is to introduce into the polymer hydroperoxides arising from oxidative destruction of PB-unsaturation; these hydroperoxides act as catalysts during subsequent u.v. irradiation. The insolubility of degraded samples of ABS is associated with the formation of cross-linked structures and occurs mainly in the PB segment. It is concluded that the degradation characteristics of ABS are essentially those of the polybutadiene component. 相似文献
997.
We report on a luminescent phenomenon in Dy3+-doped SrSiO3 long-lasting phosphor. After irradiation by a 254-nm UV lamp for 5 min, the Dy3+-doped SrSiO3 phosphor emits white light-emitting long-lasting phosphorescence for more than 1 h even after the irradiation source has been removed. Photoluminescence, long-lasting phosphorescence and thermoluminescence (TL) spectra are used to explain this phenomenon. Photoluminescence spectra reveal that the white light-emitting long-lasting phosphorescence originated from the two mixtures of Dy3+ characteristic luminescence, the 480-nm blue emission (4F9/2→6H15/2) and the 572-nm yellow emission (4F9/2→6H13/2). TL spectra shows that the introduction of Dy3+ ions into the SrSiO3 host produces a highly dense trapping level at 377 K (0.59 eV), which is responsible for the long-lasting phosphorescence at room temperature. A possible mechanism of the long-lasting phosphorescence based on the experimental results is proposed. It is considered that the long-lasting phosphorescence is due to persistent energy transfer from the electron traps to the Dy3+ ions, which creates the persistent luminescence of Dy3+ to produce the white light-emitting long-lasting phosphorescence. 相似文献
998.
Celestino Angeli Renzo Cimiraglia Maurizio Persico Alessandro Toniolo 《Theoretical chemistry accounts》1997,98(1):57-63
We discuss the “three class” approximation to full multireference perturbation CI, which greatly reduces the computational
effort by restricting the summation of diagrams to determinants belonging to a subspace of the zero-order space. In the framework
of the CIPSI algorithm, we propose a new extrapolation procedure allowing recovery of the full “two class” results. The new
procedure is applied to complete active spaces (CAS) and to individually selected zero-order spaces. Comparison with a full
two class calculation on a CAS shows a reduction of computer time of one or two orders of magnitude in the tests presented
here, with an accuracy in the order of 0.1 kcal/mol. Our procedure can thus compete with the CASPT2 algorithm, specifically
conceived to deal with CAS. In the case of selected zero-order spaces, the speed-up is less dramatic but the method still
retains its advantages.
Received: 12 June 1997 / Accepted: 31 July 1997 相似文献
999.
The reaction of alkali metal hexacyanoferrate(II/III) with (CH2)6N4 (hexamethylenetetramine, abbreviated HMT) in an acidic medium yielded crystalline compounds of stoichiometries HK2[Fe111(CN)6]·2HMT·4H2O, H2K2[Fe11(CN)6]·2HMT·4H2O, and HNa2[Fe111(CN)6]· 2HMT·5H2O. Their crystal structures are based on a packing of three molecular components: neutral and/orprotonated HMT, hexacyanoferrate, and an alkali metal ion-water cluster. The resulting three-dimensional supramolecular framework is constructed from the coordination of the alkali metal ion by aqua ligands as well as [Fe(CN)6]{n–} and HMT units, and further stabilization is achieved by hydrogen bonding between water molecules and the noncoordinated nitrogen atoms of HMT and hexacyanoferrate. 相似文献
1000.
Despite the continuing dominance of trifluoroacetic acid (TFA) as the anionic ion-pairing reagent of choice for peptide separations by reversed-phase high-performance liquid chromatography (RP-HPLC), we believe that a step-by-step approach to re-examining the relative efficacy of TFA compared to other ion-pairing reagents is worthwhile, particularly for the design of separation protocols for complex peptide mixtures, e.g., in proteomics applications. Thus, we applied RP-HPLC in the presence of different concentrations of anionic ion-pairing reagents - phosphoric acid, TFA, pentafluoropropionic acid (PFPA) and heptafluorobutyric acid (HFBA)--to a mixture of three groups of four 10-residue peptides, these groups containing peptides of +1, +3 or +5 net charge. Overall separation of the 12-peptide mixture improved with increasing reagent hydrophobicity (phosphate- < TFA- < PFPA- < HFBA-) and/or concentration of the anion, with reagent hydrophobicity having a considerably more pronounced effect than reagent concentration. HFBA, in particular, achieved an excellent separation at a concentration of just 10 mM, whereby the peptides were separated by charged groups (+1 < +3 < +5) and hydrophobicity within these groups. There was an essentially equal effect of reagent hydrophobicity and concentration on each positive charge of the peptides, a useful observation for prediction of the effect of varying counterion concentration hydrophobicity and/or concentration during optimization of peptide purification protocols. Peak widths were greater for the more highly charged peptides, although these could be decreased significantly by raising the acid concentration; concomitantly, peptide resolution increased with increasing concentration of ion-pairing reagent. 相似文献