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21.
Wuyts S De Temmerman K De Vos DE Jacobs PA 《Chemistry (Weinheim an der Bergstrasse, Germany)》2004,11(1):386-397
Acid zeolites were screened as heterogeneous catalysts for racemization of benzylic alcohols. The most promising zeolites appeared to be H-Beta zeolites, for which the optimal reaction conditions were studied in further detail. The zeolite performance was compared to that of homogeneous acids and acid resins under similar reaction conditions. In a second part of the research, H-Beta zeolites were applied in dynamic kinetic resolution (DKR) of 1-phenylethanol, which was conducted by means of a two-phase approach and which resulted in yields smoothly crossing the 50% border up to 90%, with an enantiomeric excess of >99%. To explore the applicability of this biphasic methodology, several other substrates were examined in the standard racemization reaction and in the biphasic dynamic kinetic resolution. 相似文献
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Bräuner-Osborne H Bunch L Chopin N Couty F Evano G Jensen AA Kusk M Nielsen B Rabasso N 《Organic & biomolecular chemistry》2005,3(21):3926-3936
A set of ten azetidinic amino acids, that can be envisioned as C-4 alkyl substituted analogues of trans-2-carboxyazetidine-3-acetic acid (t-CAA) and/or conformationally constrained analogues of (R)- or (S)-glutamic acid (Glu) have been synthesized in a diastereo- and enantiomerically pure form from beta-amino alcohols through a straightforward five step sequence. The key step of this synthesis is an original anionic 4-exo-tet ring closure that forms the azetidine ring upon an intramolecular Michael addition. This reaction was proven to be reversible and to lead to a thermodynamic distribution of two diastereoisomers that were easily separated and converted in two steps into azetidinic amino acids. Azetidines 35-44 were characterized in binding studies on native ionotropic Glu receptors and in functional assays at cloned metabotropic receptors mGluR1, 2 and 4, representing group I, II and III mGlu receptors, respectively. Furthermore, azetidine analogues 35, 36, and 40 were also characterized as potential ligands at the glutamate transporter subtypes EAAT1-3 in the FLIPR Membrane Potential (FMP) assay. The (2R)-azetidines 35, 37, 39, 41 and 43 were inactive in iGlu, mGlu and EAAT assays, whereas a marked change in the pharmacological profile at the iGlu receptors was observed when a methyl group was introduced in the C-4 position, compound 36 versus t-CAA. At EAAT1-3, compound 35 was inactive, whereas azetidines 36 and 40 were both identified as inhibitors and showed selectivity for the EAAT2 subtype. 相似文献
23.
Wuyts S De Temmerman K De Vos D Jacobs P 《Chemical communications (Cambridge, England)》2003,(15):1928-1929
Acid zeolites like H-Beta are efficient heterogeneous catalysts for racemization of benzylic alcohols in water; by combination of the racemization with an enzymatic kinetic resolution in a two-phase system, enantiomerically pure esters were obtained in high yield via a dynamic kinetic resolution. 相似文献
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129I Mössbauer spectroscopy was used to study the properties of129mTe labeled Ga2Te3. and alloyed (Ga2Te3)xAuy and (Ga2Te3)xAsy, sources. A satisfactory fit to the Ga2Te3 spectrum could only be obtained by introducing a distribution in the hyperfine interaction parameters. This is interpreted in favor of the hypothesis of a random distribution of the structural vacancies in the deficit cubic Ga2Te3. The addition of atomic percents of As to the compound did not change significantly the pure Ga2Te3 spectrum. The spectrum of Ga2Te3 alloyed with atomic percents of Au, on the contrary, could be fitted with only one component with a satisfactory narrow linewidth, suggesting that due to Au doping ordering is induced in the stoichiometric vacancies of the Ga2Te3 lattice structure. 相似文献
26.
D. F. Van de Vondel L. F. Wuyts G. P. Van der Kelen L. Bevernage 《Journal of Electron Spectroscopy and Related Phenomena》1977,10(4):389-392
The X-ray PES spectra of a number of manganese carbonyl complexes are reported. The binding energies are interpreted as functions of the structure and 相似文献
27.
Husted S Mikkelsen BF Jensen J Nielsen NE 《Analytical and bioanalytical chemistry》2004,378(1):171-182
Inductively coupled plasma mass spectrometry (ICP–MS) and isotope-ratio mass spectrometry (IR-MS) have been used to examine the multi-elemental composition and 15N/14N and 13C/12C isotope ratios of three spring barley (Hordeum vulgare) genotypes (Orthega, Barke, and Bartok) grown in three typical Danish agricultural soils (North Jutland, West Jutland, and East Zealand) differing in soil fertility. The aim of the study was to examine whether it was possible to generate a unique elemental fingerprint of individual barley genotypes irrespective of the elemental imprint plants had received from soils differing in fertility and agricultural practice. Multivariate statistics were used to analyze the elemental fingerprints of the barley genotypes at different times during a full growing season from early tillering to full maturity of the barley grains. Initially, 36 elements were analyzed in the plant samples but this number was subsequently reduced to 15 elements: B, Ba, C, Ca, Cu, Fe, K, Mg, Mn, N, Na, P, S, Sr, and Zn. These elements exceeded the limit of detection (LOD) for all genotypes, soil types, and plant growth stages and for these elements the accuracy was better than 90% compared with apple leaf certified reference material (CRM). Principal component analysis (PCA) separated multi-elemental data in accordance with soil type when plants of similar physiological age were compared, whereas this separation disappeared if plants of all ages were compared simultaneously. Isotope ratios (15N) of plants also proved to be a highly accurate property for classification of samples according to soil type. In contrast, the differences in 13C were too small to enable such classification. The differences in 15N among soils were so pronounced that separation of samples according to the physiological age of plants became redundant. However, 15N and the multi-elemental analysis revealed no differences between the three barley genotypes, indicating that the influence of soil chemistry and possibly also climate and agricultural practice was too large to allow an unique elemental fingerprint for the genotypes. This finding was substantiated by analyzing the multi-elemental composition of grain from two additional genotypes (Otira and Barthos) grown at the north and east locations, respectively. PCA showed not only that the elemental fingerprints of these two genotypes were similar to those of the others, but also that the soil in which the plant had been growing could be accurately predicted on the basis of the PCA scores from the genotypes Orthega, Barke, and Bartok. Similar conclusions could be drawn using 15N data. 相似文献
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Jens A. Iversen Rolf W. Berg Birgitte K. Ahring 《Analytical and bioanalytical chemistry》2014,406(20):4911-4919
Compared to traditional IR methods, Raman spectroscopy has the advantage of only minimal interference from water when measuring aqueous samples, which makes this method potentially useful for in situ monitoring of important industrial bioprocesses. This study demonstrates real-time monitoring of a Saccharomyces cerevisiae fermentation process using a Raman spectroscopy instrument equipped with a robust sapphire ball probe. A method was developed to correct the Raman signal for the attenuation caused by light scattering cell particulate, hence enabling quantification of reaction components and possibly measurement of yeast cell concentrations. Extinction of Raman intensities to more than 50 % during fermentation was normalized with approximated extinction expressions using Raman signal of water around 1,627 cm?1 as internal standard to correct for the effect of scattering. Complicated standard multi-variant chemometric techniques, such as PLS, were avoided in the quantification model, as an attempt to keep the monitoring method as simple as possible and still get satisfactory estimations. Instead, estimations were made with a two-step approach, where initial scattering correction of attenuated signals was followed by linear regression. In situ quantification measurements of the fermentation resulted in root mean square errors of prediction (RMSEP) of 2.357, 1.611, and 0.633 g/L for glucose, ethanol, and yeast concentrations, respectively. 相似文献