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11.
A simple multistep synthetic strategy to 4-substituted 1,2,3,4-tetrahydro-beta-carboline and 1,3,4,9-tetrahydro-pyrano[3,4-b]indole derivatives starting from commercially available indole 2-carboxylic acid (5) is described. The final intramolecular Michael addition promoted by catalytic amount of InBr(3) (5-10 mol %) provided the expected polycyclic compounds in excellent yields (up to 97%) both in anhydrous organic and aqueous media.  相似文献   
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Results of 16 different mass spectrometric ionization and sample-introduction methods are compared for the case of a thermally very labile antibiotic, rifapentine. These suggest that extensive thermal decomposition occurs during evaporation when the sample can come into contact with hot metal parts, usually the source housing. The intensity of the molecular ion and the extent of fragmentation depend on various parameters, such as the ionization process, positive or negative-ion detection and the type of sample introduction. The most informative methods for rifapentine seem to be ‘in-beam’ electron impact, negative ionization with particle beam and direct liquid introduction interfaces and positive- and negative-ion fast atom bombardment.  相似文献   
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Cycloolefin copolymers (COC) have recently raised much interest because of their excellent thermal and optical properties, largely determined by the chain composition and stereochemistry. Previous force‐field computations allowed us to define the main conformational characteristics of ethylene–norbornene (E–N) copolymers and to contribute to the elucidation of their microstructure on the basis of empirical relationships between conformation and 13C nuclear magnetic resonance (NMR) chemical shifts. A thorough test of ab initio 13C chemical shifts computations [gauge‐invariant atomic orbitals (GIAO)] on known cases shows that the agreement with experimental data is quite good, especially with the MPW1PW91 density functional theory (DFT), using the 6‐311+G(2d,p) basis set on properly energy‐minimized structures. We applied this method on proper model compounds to confirm the signal assignment of the spectra of E–N copolymers in the presence of norbornene microblocks, where strong effects arising from ring distortions are expected to occur. The results nicely confirm the latest assignment of norbornene signals belonging to ENNE sequences. This shows the great potentialities of GIAO/DFT computations with regard to complex spectra interpretation and polymer microstructural investigations. © 2002 Wiley Periodicals, Inc. Int J Quantum Chem, 2002  相似文献   
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Multivariate statistical techniques were applied to the UV spectra of a series of solutions at pH 12 containing a fixed concentration (30 mM) of beta-cyclodextrin (beta-CD) and a fixed concentration (15 mM) of 2-phenylglycine (phi-Gly) with various known enantiomeric compositions. Multivariate correlation of the spectral data for the solutions containing the phi-Gly/beta-CD guest-host complexes with the known enantiomeric composition of the phi-Gly samples was accomplished by partial-least-squares regression. When the multivariate model was used to predict the enantiomeric purity of a test set of samples over the mol fraction range of 0.5-0.9 R-phi-Gly, the average magnitude of the relative errors in the mol fraction determination of enantiomeric composition was 3%. A plot of the enantiomeric composition predicted by the model versus the known enantiomeric composition of the calibration set gave a straight line with a correlation coefficient of 0.955, a slope of 1.05, and an offset of 5.61 x 10-4.  相似文献   
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The structures of the title compounds bearing a five-, six- or seven-membered A ring have been investigated by uv and 1H and 13C nmr spectroscopy. The imine-enol-enamine (I-II-III) tautomerism of these compounds depends greatly on the ring size. A significant solvent-dependence is observed only for the five-membered-ring compounds 1 and 2 , which in ethanolic solution exist predominantly in the imine form I, and in chloroform solution in the enol form II. The compounds with a six-membered A ring, 3 and 4 , are mainly in the enamine form III. On protonation, 3 and 4 change into the E and Z isomeric mixture of the enol tautomer II. The seven-membered-ring compound 5 is a mixture of the imine I and the enamine III tautomers.  相似文献   
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More than 100 samples of blue-green algae products (consisting of Aphanizomenon, Spirulina, and unidentified blue-green algae) in the form of pills, capsules, and powders were collected from retail outlets from across Canada. The samples were extracted with 75% methanol in water and centrifuged to remove solids. Aliquots of the extracts along with spiked blank sample extracts were sent to each participating laboratory and independently analyzed for microcystins by enzyme-linked immunosorbent assay (ELISA), protein phosphatase inhibition assay, and by liquid chromatography-tandem mass spectrometry (LC-MS/MS) after sample cleanup using C18 solid-phase extraction. The results obtained by ELISA and LC-MS/MS agreed very well over a concentration range of about 0.5-35 microg/g. The colorimetric phosphatase results generally agreed with the other 2 methods. While the 2 biochemical assays measured total microcystin content compared with a standard of microcystin LR, the LC-MS/MS method measured specific microcystins (LA, LR, RR, YR) using external standards of these for identification and quantitation. Microcystin LR was found in all positive samples by LC-MS/MS. Microcystin LA was the only other microcystin found in the samples analyzed. These 2 microcystins represent essentially all the microcystins that were present in the extracts. Otherwise, the LC-MS/MS results would have been significantly lower than the results of the biochemical assays had other unknown microcystins been present.  相似文献   
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