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991.
Aldous DJ Batsanov AS Yufit DS Dalençon AJ Dutton WM Steel PG 《Organic & biomolecular chemistry》2006,4(15):2912-2927
Flash vacuum pyrrolysis of vinyl epoxides provides cis-dihydrofuran carboxylic esters in good yields and diastereoselectivities, which, on base-promoted epimerisation afford the complementary trans series. The compounds provide a viable template for a Lewis acid promoted cyclisation to provide the 2,6-diaryl-3,7-dioxabicyclo[3.3.0]octane core found in the furofuran series of natural lignans. This strategy is stereodivergent and can be controlled to provide the exo-exo, exo-endo or endo-endo stereochemistries. The approach has been exemplified in syntheses of the sesamyl furofurans (+/-)-epiasarinin and (+/-)-asarinin. 相似文献
992.
Fillaux F Romain F Limage MH Leygue N 《Physical chemistry chemical physics : PCCP》2006,8(37):4327-4336
We compare Raman and infrared spectra of the nuOH/OD modes in benzoic acid crystal powders at 7 K. The extremely sharp Raman bands contrast to the broad infrared profiles and suggest adiabatic separation of hydrogen (deuterium) dynamics from the crystal lattice. There is no evidence of any proton-proton coupling term. The assignment scheme is consistent with a quasisymmetric double-minimum potential, largely temperature independent. Tunnel splitting is a major band shaping mechanism, in addition to anharmonic coupling with lattice modes. The proton/deuteron dynamics are rationalized with nonlocal pseudoparticles and extended states. We propose a symmetry-related damping mechanism to account for the broad infrared profiles, as opposed to the sharp Raman bands. We assign spectral features to distinct interconversion mechanisms based on either pseudoparticle transfer or adiabatic pairwise transfer. We establish close contacts with theoretical models based on first-principles calculations. 相似文献
993.
It has been experimentally observed that trivalent ions are capable of promoting compaction of semi-flexible polyelectrolyte chains. In this work we perform Monte Carlo simulations on single chain model systems with varying chain size and stiffness and evaluate the action of multivalent salt on the chain conformation. It is observed that longer chains tend to achieve relatively more compact conformations than shorter ones, and the dimensions of the collapsed structures do not significantly vary with contour length. The influence of contour length and intrinsic stiffness in the process of ion condensation is studied by analysis of the ion-ion nearest-neighbor distribution. The general trend is an increase of the degree of ion condensation as the chain length increases, in accordance with experimental evidence. A decreased importance of end-effects and, especially, larger volume charge densities are responsible for such behavior. The influence of chain stiffness is nontrivial, and depends on salt concentration. The results emphasize the complex nature of ion-correlation phenomena in flexible or semi-flexible chains and call for the development of more sophisticated analytical theories. 相似文献
994.
The preparation of a dendritic graft polymer by a very efficient synthesis of polyglycerol directly on a polystyrene resin is presented. This one-step process can be performed on a multigram scale to provide a chemically stable polymeric support. The resulting hybrid polymers were fully characterized by diverse analytical methods (NMR, IR, ESEM, UV detection of cleaved protecting groups, and mass-spectrometric methods). They combine a high loading capacity (up to 4.3 mmol g(-1)) with good swelling properties in a wide range of solvents (including water), which is the major drawback for many existing solid phase supports. In comparison to the widely employed PEGylated resins, these hybrid materials offer a 10-fold higher loading capacity. Their suitability as supports for organic synthesis and for the immobilization of reagents has been demonstrated. These materials also swell in water, and consequently, it should be possible to use these new hybrid materials for synthesis in protic solvents. 相似文献
995.
The structural, dynamic, and thermodynamic properties of an excess electron interacting with an alkali cation (Na+, K+, Li+) in bulk water were investigated by means of a mixed quantum-classical molecular dynamics simulation technique. This study includes a reparametrization of the electron-cation pseudopotentials. The free energy calculations for all three systems show that a contact electron-cation pair can be observed, which is either as stable as the dissociated pair (Li+) or more stable by only a few kT (Na+, K+). Given that the dissociation barrier is also quite small, we suggest that the average cation-electron distance in the experiments at room temperature will not depend on this free energy profile but rather on the minimization of the Coulombic repulsive interaction between like charges in the solvent medium. This enables us to compare the present molecular dynamics simulations with the spectroscopic data obtained for different ionic strengths. The overall trend of the UV-vis hydrated absorption spectra, namely, the shift toward shorter wavelengths at high ionic strengths, is fairly well reproduced. This confirms our hypothesis of statistical distribution of the cations and solvated electrons. 相似文献
996.
A comprehensive normal phase system LC-reversed phase LC (NPLC x RPLC) was evaluated for the separation of a pharmaceutical mixture and citrus oil extracts. NPLC was performed on a 25 cm x 1 mm ID x 5 microm dp diol phase. In the second dimension, an RP 18 monolithic column (10 cm L x 4.6 mm ID x 2 microm macropore size) and an octadecyl silicagel-packed column (5 cm L x 4.6 mm ID x 3.5 microm dp) were applied for the analyses of the pharmaceutical sample and the citrus oil extracts, respectively. A two-position/ten-port switching valve was used as interface. Under optimised LC conditions, the high degree of orthogonality between NP and RP resulted in peak capacities of 300 for the pharmaceutical sample and of 450 for the citrus oil extract composed of lemon and orange oil. Despite the features of NPLC x RPLC, several shortcomings related with the solvent incompatibility between the two LC modes were identified and the practical consequences were discussed. 相似文献
997.
Antignac JP Marchand P Gade C Matayron G Qannari el M Le Bizec B Andre F 《Analytical and bioanalytical chemistry》2006,384(1):271-279
Polychlorinated dibenzo-p-dioxins (PCDD) and polychlorinated dibenzofurans (PCDF) are widely recognized by the scientific community as persistent organic
pollutants due to their toxicity and adverse effects on wildlife and human health. The actual regulation dedicated to the
monitoring of dioxins in food is based on the measurement of 17 congener concentrations. The final result is reported as a
toxic equivalent value that takes into account the relative toxicity of each congener. This procedure can minimize the qualitative
information available from the abundances of each PCDD/PCDF congener: the characteristic contamination profile of the sample.
Multivariate statistical techniques, such as principal component analysis (PCA) or linear discriminant analysis (LDA), represent
an interesting way to investigate this qualitative information. Nevertheless, they have only been applied to the analysis
of contamination data from food products and biological matrices infrequently. The objective of the present study was to analyze
a large data set from dioxin analyses performed on various food products of animal origin. The results demonstrate the existence
of differences in congener-specific patterns between the analyzed samples. Variability was first demonstrated in terms of
the food type (fish, meat, milk, fatty products). Then a variability was observed that was related to the specific animal
species for meat and milk samples (bovine, ovine, porcine, caprine and poultry). Some practical applications of these results
are discussed. The origin(s) of the observed differences, as well as their significance, now remain to be investigated, both
in terms of environmental factors and transfer through living organisms. A better knowledge of the relation between a contamination
profile and its specific source and/or food product should be of great interest to scientists working in the fields of contaminant
analysis, toxicology and metabolism, as well as to regulatory bodies and risk assessors in charge of final decisions regarding
the eventual hazards associated with theses substances. 相似文献
998.
A method based on solid-phase microextraction (SPME) coupled with GC and ion trap tandem mass spectrometry has been developed
for the analysis of nine herbicides and degradation products, among the most frequently found in natural water. A polydimethylsiloxane–divinylbenzene
(PDMS–DVB)-coated fiber was selected to extract the analytes directly from the samples over the 0.01–1 μg L−1 concentration range. Optimization of manual and automated SPME was performed on the basis of desorbed amounts, via various
factorial experiment designs. Of the two modes, the automated one was found to be the most efficient. Memory effect was avoided
owing to the 10-min fiber desorption time. Limits of detection reached down to below 0.01 μg L−1 and repeatability ranged from 3 to 15% in natural water. A validation study was conducted involving the quantitation of the
target compounds in Seine water with SPME/GC–MS-MS external calibration. 相似文献
999.
Loison JC Bergeat A Caralp F Hannachi Y 《The journal of physical chemistry. A》2006,110(50):13500-13506
The reactions of the CH radical with several alkanes were studied, at room temperature, in a low-pressure fast-flow reactor. CH(X2Pi, v = 0) radicals were obtained from the reaction of CHBr(3) with potassium atoms. The overall rate constants at 300 K are (0.76 +/- 0.20) x 10(-10) [Fleurat-Lessard, P.; Rayez, J. C.; Bergeat, A.; Loison, J. C. Chem. Phys. 2002, 279, 87],1 (1.60 +/- 0.60) x 10(-10)[Galland, N.; Caralp, F.; Hannachi, Y.; Bergeat, A.; Loison, J.-C. J. Phys. Chem. A 2003, 107, 5419],2 (2.20 +/- 0.80) x 10(-10), (2.80 +/- 0.80) x 10(-10), (3.20 +/- 0.80) x 10(-10), (3.30 +/- 0.60) x 10(-10), and (3.60 +/- 0.80) x 10(-10) cm3 molecule(-1) s(-1), (errors refer to +/-2sigma) for methane, ethane, propane, n-butane, n-pentane, neo-pentane, and n-hexane respectively. The experimental overall rate constants correspond to those obtained using a simple classical capture theory. Absolute atomic hydrogen production was determined by V.U.V. resonance fluorescence, with H production from the CH + CH4 reaction being used as a reference. Observed H branching ratios were for CH4, 1.00[Fleurat-Lessard, P.; Rayez, J. C.; Bergeat, A.; Loison, J. C. Chem. Phys. 2002, 279, 87];1 C(2)H(6), 0.22 +/- 0.08 [Galland, N.; Caralp, F.; Hannachi, Y.; Bergeat, A.; Loison, J.-C. J. Phys. Chem. A 2003, 107, 5419];2 C(3)H(8), 0.19 +/- 0.07; C(4)H(10) (n-butane), 0.14 +/- 0.06; C(5)H(12) (n-pentane), 0.52 +/- 0.08; C(5)H(12) (neo-pentane), 0.51 +/- 0.08; C(5)H(12) (iso-pentane), 0.12 +/- 0.06; C(6)H(14) (n-hexane), 0.06 +/- 0.04. 相似文献
1000.
Bayrakçeken F Telatar Z Ari F Tunçyürek L Karaaslan I Yaman A 《Spectrochimica acta. Part A, Molecular and biomolecular spectroscopy》2006,65(1):143-146
The alpha-methallyl free radical is formed in the flash photolysis of 3-methylbut-1-ene, and cis-pent-2-ene in the vapor phase, and then subsequent reactions have been investigated by kinetic spectroscopy and gas-liquid chromatography. The photolysis flash was of short duration and it was possible to follow the kinetics of the radicals' decay, which occurred predominantly by bimolecular recombination. The measured rate constant for the alpha-methallyl recombination was (3.5+/-0.3) x 10(10) mol(-1) ls(-1) at 295+/-2K. The absolute extinction coefficients of the alpha-methallyl radical are calculated from the optical densities of the absorption bands. Detailed analysis of related absorption bands and lifetime measurements in the original alpha-methallyl high-resolution discrete absorption spectrum image were also carried out by image processing techniques. 相似文献