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排序方式: 共有118条查询结果,搜索用时 15 毫秒
81.
Prélot B Villiéras F Pelletier M Gérard G Gaboriaud F Ehrhardt JJ Perrone J Fedoroff M Jeanjean J Lefèvre G Mazerolles L Pastol JL Rouchaud JC Lindecker C 《Journal of colloid and interface science》2003,261(2):244-254
In the framework on a study of the acido-basic and sorption properties of iron oxides, a thorough characterization of two types of goethite powders was performed in several laboratories joined in a common project. Chemical analysis by ICPAES; high-resolution SEM, TEM, and AFM observations; XRD with line width analysis; and argon and nitrogen sorption isotherms were used for that purpose. The main crystallographic faces of goethite particles could be identified as {001}, {101}, and {121}, and their abundance correlated with the distribution of low-pressure argon adsorption local isotherms. These results will be very useful for further studies on the relationship between surface reactivity in aqueous solution and orientation of solid surfaces. 相似文献
82.
∝-methyl ∝-functionalized (CO2CH3, CN, CH2OH and CH2Cl) cyclopentanones when irradiated by UV light give title compounds : 5-substituted 4-hexen 1-al as a mixture of E and Z isomers. A comparison of the photochemical behaviour of this cyclopentanones and a simple and efficient chemical transformation of the isomers Z in the more demanded isomers E are described. 相似文献
83.
Jean-Claude Barrire Jeanine Clophax Stephan D. Gro Marc Vuilhorgne 《Helvetica chimica acta》1983,66(5):1392-1408
The cyclopentenecarbaldehyde 1a , acetals 2a , 2b and the cyclopentenone 2c have been transformed through regio and stereocontrolled reactions into a variety of enantiomerically pure substituted cyclopentanes. Using appropriately selected Wittig reagents, aldehyde 1a furnished the condensation products 3 , 4 , 5 . Michael addition of diethyl malonate on the α,β-unsaturated aldehyde 1a under phasetransfer conditions led efficiently to 7 . Reduction of the cyclopentenone 2c gave 21 in high yield. The cyclopentenes 2a , 2b and 23 , submitted to hydroboration-oxidation furnished the cyclopentanols 10 , 13 and 24 , respectively, in 30, 70 and 50% yields, reflecting the substitution pattern of the starting alkenes. The salient feature of these reactions is the stereospecificity due to the chiral centre of the molecules 1a , 2a , 2b and 2c , leading to compounds with two, three and four asymmetric centres. The straightforward synthesis of 11α-hydroxy-13-oxaprostanoic acid 20 is described and an approach towards the preparation of 9α, 11α-dihydroxy-13-oxaprostanoic acid 34 is also presented. The structure of these products has been determined by 1H- and 13C-NMR spectroscopy. 相似文献
84.
Z-α-acylaminocinnamate esters were hydrogenated with neutral rhodium(I) complexes containing (1S, 2S)-trans-1,2-bis(diphenylphosphinomethyl)cyclohexane. Increasing the steric bulk of the alcohol moiety of the ester function results in increased enantioface differentiation in favor of the re-si prochiral face to yield an excess of the S-amino acid derivatives. In the series of N-acetylphenylalanine ester products (resulting from hydrogenation of Z-α-acetamidocinnamate esters) the optical purity increased from 1% ee-(R) [Me]; 20% ee-(S) [Et]; 47% ee-(S) [i-Pr]; to 58% ee-(S) [t-Bu]. Increasing the steric bulk of the acyl function (NHCOR, where R is an alkyl moiety) favors the reduction of the si-re prochiral face [in the methyl ester substrates] to yield an excess of the R-amino acid derivatives. In the series of N-acylphenylalanine methyl ester products (resulting from hydrogenation of Z-methyl α-acylaminocinnamates) the optical purity increased from 1% ee-(R) [Me]; 13% ee-(R) [i-Pr]; to 15% ee-(R) [t-Bu and 1-adamantyl]. The α-formamido and α-benzamido substrates gave hydrogenation products having 22% ee-(R) [H] and 35% ee-(R) [Ph]. In the corresponding free acids, increasing the steric bulk of the acyl function (NHCOR, where R is an alkyl moiety) results in almost no change in the optical purity of the reduction products. In the series of N-acylphenyl-alanine products (resulting from hydrogenation of Z-α-acylaminocinnamic acids) the optical purity was 35% ee-(S) [Me]; 31% ee-(S) [i-Pr]; 33% ee-(S) [t-Bu]; and 35% ee-(S) [1-adamantyl]. The α-benzamido substrate gave a hydrogenation product having 8% ee-(S). 相似文献
85.
A general framework is presented for the interpretation of NMR relaxation data of proteins. The method, termed isotropic reorientational eigenmode dynamics (iRED), relies on a principal component analysis of the isotropically averaged covariance matrix of the lattice functions of the spin interactions responsible for spin relaxation. The covariance matrix, which is evaluated using a molecular dynamics (MD) simulation, is diagonalized yielding reorientational eigenmodes and amplitudes that reveal detailed information about correlated protein dynamics. The eigenvalue distribution allows one to quantitatively assess whether overall and internal motions are statistically separable. To each eigenmode belongs a correlation time that can be adjusted to optimally reproduce experimental relaxation parameters. A key feature of the method is that it does not require separability of overall tumbling and internal motions, which makes it applicable to a wide range of systems, such as folded, partially folded, and unfolded biomolecular systems and other macromolecules in solution. The approach was applied to NMR relaxation data of ubiquitin collected at multiple magnetic fields in the native form and in the partially folded A-state using MD trajectories with lengths of 6 and 70 ns. The relaxation data of native ubiquitin are well reproduced after adjustment of the correlation times of the 10 largest eigenmodes. For this state, a high degree of separability between internal and overall motions is present as is reflected in large amplitude and collectivity gaps between internal and overall reorientational modes. In contrast, no such separability exists for the A-state. Residual overall tumbling motion involving the N-terminal beta-sheet and the central helix is observed for two of the largest modes only. By adjusting the correlation times of the 10 largest modes, a high degree of consistency between the experimental relaxation data and the iRED model is reached for this highly flexible biomolecule. 相似文献
86.
Trujillo C Mó O Yañez M Tortajada J Salpin JY 《The journal of physical chemistry. B》2008,112(17):5479-5486
The gas-phase reactions between Ca(2+) and selenourea were investigated by means of electrospray/tandem mass spectrometry techniques. The MS/MS spectra of [Ca(selenourea)](2+) complexes show intense peaks at m/z 43, 121, 124, and 146 and assigned to monocations produced in different coulomb explosion processes. The structures and bonding characteristics of the stationary points of the [Ca(selenourea)](2+) potential energy surface (PES) were theoretically studied by DFT calculations carried out at the B3LYP/6-311+G(3df,2p)//B3LYP/6-311+G(d,p) level. The analysis of the topology of this PES allows identification of H(2)NCNH(+), CaSeH(+), selenourea(+). and CaNCSe(+) ion peaks at m/z 43, 121, 124, and 146, respectively. The reactivity of selenourea and the topology of the corresponding potential energy surface mimic that of thiourea. However, significant dissimilarities are found with respect to urea. The dissociative electron-transfer processes, not observed for urea, is one of the dominant fragmentations for selenourea, reflecting its much lower ionization energy. Similarly, the coulomb explosions yielding CaXH(+) + H(2)NCNH(+) (X = O or Se), which for urea are not observed, are very favorable for selenourea. Finally, while in urea the loss of NH(3) competes with the formation of NH(4+), for selenourea the latter process is clearly dominant. 相似文献
87.
José L. F. C. Lima C. Delerue-Matos M. Carmo M. C. V. F. Vaz Jeanine Silva 《Fresenius' Journal of Analytical Chemistry》1999,364(3):266-269
A flow injection analysis (FIA) system with potentiometric detection has been developed for the determination of citric acid
in commercial fruit juices using a copper-selective tubular electrode. It consists of the complexation of citrate ion with
copper (II) ion, monitoring the free copper (II) concentration. Linear relationships between the potential and log concentrations
of citric acid in the range of 1 × 10–3 mol/L – 1 × 10–2 mol/L were attained with samples injected in the system without prior treatment. Repeatability was determined by assessing
the relative standard deviation for ten replicate injections of different juice samples which varied from 1.2% to 3.0%. The
results provided by the automated system were compared with those of an enzymatic conventional method used for the analysis
of citric acid in food and a relative deviation of less than 4.0% was found. Recovery trials resulted in values from 97.0%
to 101.0%. The system allows a sampling frequency of 60 samples/h.
Received: 22 October 1998 / Revised: 14 December 1998 / Accepted: 16 December 1998 相似文献
88.
J. -P. Morizur B. Desmazières J. Chamot-Rooke V. Haldys P. Fordham J. Tortajada 《Journal of the American Society for Mass Spectrometry》1998,9(7):731-734
The use of copper ions for chemical ionization (CI) coupled with gas chromatography/mass spectrometry (GC/MS) of hydrocarbons is reported. Cu+?CI was performed in a high-pressure, fast atom bombardment ion source coupled with both a gas chromatograph and a mass spectrometer. The suitability of the Cu+?CI method is illustrated by the analysis of pure alkylbenzenes, alkylthiophenes, octenes, and by the analysis of a light mixture of aromatic hydrocarbons. The Cu+?CI/GC mass spectra display an abundant [M+63Cu]+ ion, together with fragmentations, that are of structural interest. The detection limit for isobutylbenzene, taken as model compound, is 100 times lower than that for electron ionization. 相似文献
89.
Lamsabhi AM Mó O Yáñez M Salpin JY Haldys V Tortajada J Guillemin JC 《The journal of physical chemistry. A》2008,112(42):10509-10515
The reaction of aminoacrylonitrile, a species of astrochemical interest, with Ni(+)((2)D(5/2)) was investigated by means of mass spectrometry techniques and density functional theory calculations. The dominant fragmentations in the MIKE spectrum correspond to the loss of [C2,N,H3], HCN, and NH3, the loss of H2 being very minor. The structure and bonding of the different aminoacrylonitrile-Ni(+) complexes were investigated at the B3LYP/6-311G(d,p) level of theory. The same approach was employed in our survey of the corresponding potential energy surface. This survey indicates that the [C2,N,H3] neutral product can be formed either as ketenimine (CH2CNH) or acetonitrile. The formation of the latter is significantly more exothermic but involves slightly higher activation barriers; so very likely, both isomers are produced along the reaction process. The lost of HNC is not competitive with the loss of HCN, because when the former is formed the products lie higher in energy and the corresponding mechanisms involve energy barriers above the entrance channel. The loss of NH3 is associated with the formation of a complex between cyanoacetylene, HCCCN, which is very abundant in the interstellar media, and Ni(+). 相似文献
90.
Let K be an algebraic number field. We discuss the problem of counting the number of integral ideals below a given norm and obtain effective error estimates. The approach is elementary and follows a classical line of argument of Dedekind and Weber. The novelty here is that explicit error estimates can be obtained by fine tuning this classical argument without too much difficulty. The error estimate is sufficiently strong to give the analytic continuation of the Dedekind zeta function to the left of the line R(s)=1 as well as explicit bounds for the residue of the zeta function at s=1. 相似文献