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11.
VladimirA. Azov Franois Diederich Yoriko Lill Bert Hecht 《Helvetica chimica acta》2003,86(6):2149-2155
We report the synthesis of modified Cram‐type cavitands bearing one or two fluorescent labels for single‐molecule spectroscopic studies of vase? kite conformational switching (Scheme 3). Syntheses were performed by stepwise bridging of the four couples of neighboring H‐bonded OH groups of resorcin[4]arene bowls (Schemes 2 and 3). The new substitution patterns enable the construction of a large variety of future functional architectures. 1H‐NMR Investigations showed that the new partially and differentially bridged cavitands feature temperature‐ and pH‐triggered vase? kite conformational isomerism similar to symmetrical cavitands with four identical quinoxaline bridges (Table). It was discovered that vase? kite switching of cavitands is strongly solvent‐dependent. 相似文献
12.
Groothaert MH Smeets PJ Sels BF Jacobs PA Schoonheydt RA 《Journal of the American Chemical Society》2005,127(5):1394-1395
This work reports on the capability of the O2-activated Cu-ZSM-5 and Cu-MOR zeolites to selectively convert methane into methanol at a temperature of 398 K. A strong correlation between (i) the activity and (ii) the intensity of the 22 700 cm-1 UV-vis band, assigned to the bis(mu-oxo)dicopper core, is found (i) as a function of the reaction temperature, (ii) as a function of the Cu loading of the zeolite, and (iii) in comparison to other Cu materials. These three lines of evidence firmly support the key role of the bis(mu-oxo)dicopper core in this selective, low-temperature hydroxylation of methane. 相似文献
13.
Summary The enantioseparation of amphetamine, methamphetamine and various ring-substituted amphetamines by use of a chiral stationary phase carrying immobilized native -cyclodextrin (-CyD) selectors is reported. The system is evaluated for resolving the specified compounds directly without any derivatization and after derivatization with phenyl isothiocyanate (PITC), naphthyl isothiocyanate (NITC) and 6-aminoquinolyl-N-hydroxysuccinimidyl carbamate (AQC). This direct enantioseparation is compared with the features of indirect separation of diasteromeric derivatives after reaction with the optically pure Marfey's reagent employing a simple non-chiral alkyl-silica (RP-8) column. A selection of those methods best suited for each single amphetamine is given.Seventeen different samples of amphetamine, confiscated by the Swedisch police, were analyzed with respect to their enantiomeric composition. Within this set of samples synthesized by the same method no significant deviation from a racemic ratio could be observed. 相似文献
14.
Grandjean D Beale AM Petukhov AV Weckhuysen BM 《Journal of the American Chemical Society》2005,127(41):14454-14465
The hydrothermal crystallization of CoAPO-5 molecular sieves has been studied using time-resolved in-situ SAXS/WAXS, UV-vis, Raman, and XAS. Data collected during heating to 180 degrees C allowed the observation of different steps occurring during the transformation of the amorphous gel into a crystalline material from a macroscopic and atomic perspective. Raman spectroscopy detected the initial formation of Al-O-P bonds, whereas SAXS showed that these gel particles had a broad size distribution ranging from ca. 7 to 20 nm before crystallization began. WAXS showed that this crystallization was sharp and occurred at around 160 degrees C. Analysis of the crystallization kinetics suggested a one-dimensional growth process. XAS showed that Co(2+) transformed via a two-stage process during heating involving (i) a gradual transformation of octahedral coordination into tetrahedral coordination before the appearance of Bragg peaks corresponding to AFI, suggesting progressive incorporation of Co(2+) into the poorly ordered Al-O-P network up to ca. 150 degrees C, and (ii) a rapid transformation of remaining octahedral Co(2+) at the onset of crystallization. Co(2+) was observed to retard crystallization of AFI but provided valuable information regarding the synthesis process by acting as an internal probe. A three-stage, one-dimensional crystallization mechanism is proposed: (i) an initial reaction between aluminum and phosphate units forming a primary amorphous phase, (ii) progressive condensation of linear Al-O-P chains forming a poorly ordered structure separated by template molecules up to ca. 155 degrees C, and (iii) rapid internal reorganization of the aluminophosphate network leading to crystallization of the AFI crystal structure. 相似文献
15.
The epoxidation of propene over gold/titania based catalysts was investigated using different techniques. Infrared spectroscopic information showed that one key step in the reaction mechanism is a reaction catalyzed by gold between titania surface groups and propene. In this reaction step, a bidentate propoxy species is formed on titania. This species adsorbs strongly on the catalyst, and it is the same species which is formed when propene oxide adsorbs on titania. Gravimetrical adsorption experiments and catalytic tests show that product adsorption and desorption are important factors determining the catalytic activity and the catalyst stability. By combining the information from different techniques, a kinetic mechanism is proposed. 相似文献
16.
Mueller JA Cowell A Chandler BD Sigman MS 《Journal of the American Chemical Society》2005,127(42):14817-14824
A kinetic investigation into the origin of enantioselectivity for the Pd[(-)-sparteine]Cl(2)-catalyzed aerobic oxidative kinetic resolution (OKR) is reported. A mechanism to account for a newly discovered chloride dissociation from Pd[(-)-sparteine]Cl(2) prior to alcohol binding is proposed. The mechanism includes (1) chloride dissociation from Pd[(-)-sparteine]Cl(2) to form cationic Pd(-)-sparteine]Cl, (2) alcohol binding, (3) deprotonation of Pd-bound alcohol to form a Pd-alkoxide, and (4) beta-hydride elimination of Pd-alkoxide to form ketone product and a Pd-hydride. Utilizing the addition of (-)-sparteine HCl to control the [Cl(-)] and [H(+)] and the resulting derived rate law, the key microscopic kinetic and thermodynamic constants were extracted for each enantiomer of sec-phenethyl alcohol. These constants allow for the successful simulation of the oxidation rate in the presence of exogenous (-)-sparteine HCl. A rate law for oxidation of the racemic alcohol was derived that allows for the successful prediction of the experimentally measured k(rel) values when using the extracted constants. Besides a factor of 10 difference between the relative rates of beta-hydride elimination for the enantiomers, the main enhancement in enantiodetermination results from a concentration effect of (-)-sparteine HCl and the relative rates of reprotonation of the diastereomeric Pd-alkoxides. 相似文献
17.
V. N. Fedoseyev Y. Jading O. C. Jonsson R. Kirchner K. -L. Kratz M. Krieg E. Kugler J. Lettry T. Mehren V. I. Mishin H. L. Ravn T. Rauscher F. Scheerer O. Tengblad P. Van Duppen A. Wöhr 《Zeitschrift für Physik A Hadrons and Nuclei》1995,353(1):9-10
The continuum part of the6Li (a,a)6Li (1.47–2.47 MeV) scattering data at Ea=50 MeV are extracted in two discretized bins. Coupled-channel calculations are carried out coupling the 1+ ground state of6Li with both the resonant, 3+
1 state, and two non-resonant continuum states. The discretized continuum of the6Li (p,p)6Li (1.75–3.25 MeV) scattering data at Ep=65 MeV are also analysed on the same footing. In both the cases the effect of coupling is found to be minimal. 相似文献
18.
Pyrolyses of acrylonitrile-methacrylic acid copolymers and their sodium salts were studied under inert atmosphere at various heating rates using thermogravimetric analysis coupled with gas liquid chromatography, thermal volatilization analysis, differential scanning calorimetry and flash pyrolysis coupled with GLC and eventually mass spectrometric analysis. The mechanisms of the nitrile oligomerization and subsequent chain scission, giving rise to volatilization, are discussed in connection with the sequence distribution of monomeric units in the copolymers. 相似文献
19.
-Methyl 2,3-anhydro-4,6-O-benzylidene-α-D-allopyranoside undergoes the Wadsworth- Emmons cyclopropanation with phosphonopropionate to give a cyclopropyl carboxylate which is processed to give the gem-dimethylcyclopropano pyranoside. The glycosylic acetal of this substance is readily hydrolyzed by boiling water, and the resulting cis-cyclopropane carboxaldehyde may be epimerized quantitatively to the trans-analog by treatment with sodium methoxide. These aldehydes are now converted into the (+)- and (-)-chrysanthemum dicarboxylic acids, respectively, by the same sequence of reactions involving (a) olefination with methyl 2-(triphenylphosphoranylidene)propionate, (b) hydro- lysis of the benzylidine ring and cleavage of the resulting triol with sodium metaperiodate, and (c) oxidation of the resulting aldehyde with silver I oxide. In the case of the (+)-enantiomer the last reaction is proceeded by epimerization. The overall yields from the D-allopyranoside are respectively 27%, in 10 steps for the (+)-enantiomer, and 24%, in 10 steps for the (-)-enantiomer, from the known epoxide 7. 相似文献
20.
Single-site heterogeneous Cr-based catalyst for the selective trimerisation of ethylene 总被引:1,自引:0,他引:1
TAC-Cr3+/SiO2 complexes are highly active and selective ethylene trimerisation catalysts and possess single-site catalytic behaviour, an unusual property for heterogeneous catalysts. 相似文献