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991.
Mossambine (6) was obtained by a six-step reaction sequence from the indoloazepine ester 7. Radical cyclization of the tetracyclic vinyl iodide 12a provided a racemic pentacyclic ketone 16E, which could be converted to either enantiomer by condensation with (S or R)-N,S-dimethyl-S-phenylsulfoximine and selective pyrolysis of the resulting diastereomeric alcohols 18 and 19 or 20 and 21. Selective reductions of the resolved (or racemic) ketone 16E provided mossambine (6) and its hydroxy epimer 17. 相似文献
992.
In recent years, several newer designer drugs of the so-called 2C series such as 2C-D, 2C-E, 2C-P, 2C-B, 2C-I, 2C-T-2, and 2C-T-7 have entered the illicit drug market as recreational drugs. Some fatal intoxications involving 2C-T-7 have been reported. Only scarce data have been published about analyses of these substances in human blood and/or plasma. This paper describes a method for screening and simultaneous quantification of the above-mentioned compounds and their analog mescaline in human blood plasma. The analytes were analyzed by gas chromatography/mass spectrometry in the selected-ion monitoring mode, after mixed-mode solid-phase extraction (HCX) and derivatization with heptafluorobutyric anhydride. The method was fully validated according to international guidelines. Validation data for 2C-T-2 and 2C-T-7 were unacceptable. For all other analytes, the method was linear from 5 to 500 microg/L and the data for accuracy (bias) and precision (coefficient of variation) were within the acceptance limits of +/-15% and <15%, respectively (within +/-20% and <20% near the limit of quantification of 5 microg/L). 相似文献
993.
The liquid secondary ion mass spectra of 15-crown-5 in the presence of equimolecular mixtures of three alkali metal salts show large changes in the relative abundances of the 15-crown-5-cation complexes formed, depending on the relative concentrations of ligand and salts. These variations are due either to various desorption rates of the cationized species or to different affinities of 15-crown-5 toward the alkali metal cations. An original method allowing discrimination between desorption and complexation effects on the relative abundance of ligand-metal complex ions is described and can be applied for the calculation of their stability constants. The spectral data obtained using two different matrices demonstrate that the matrix polarity has a very important effect on the two parameters considered, i.e. the stability constants of the 15-crown-5-cation complexes and their desorption rates. 相似文献
994.
The syntheses of [4]rotane and polycyclopropylspiranic derivatives are reported. One route involves the formation of cyclopropane rings from C4-acyloins; a second route uses the dimerisation of bicyclopropylidene. Spectroscopic data do not point to any particular electronic interactions between cyclopropane rings in these compounds. 相似文献
995.
Denis N. Buckley Elizabeth Harvey Sung-Nee G. Chu 《Monatshefte für Chemie / Chemical Monthly》2002,133(6):785-798
Summary. Film formation on compound semiconductors under anodic conditions is discussed. The surface properties of InP electrodes
were examined following anodization in an (NH4)2S electrolyte. The observation of a current peak in the cyclic voltammetric curve was attributed to selective etching of the
substrate and a film formation process. AFM images of samples anodized in the sulfide solution revealed surface pitting. Thicker
films formed at higher potentials exhibited extensive cracking as observed by optical and electron microscopy, and this was
explicitly demonstrated to occur ex situ rather than during the electrochemical treatment. The composition of the thick film was identified as In2S3 by EDX and XPS. The measured film thickness varies linearly with the charge passed, and comparison between experimental thickness
measurements and theoretical estimates for the thickness indicate a porosity of over 70%. Cracking is attributed to shrinkage
during drying of the highly porous film and does not necessarily imply stress in the wet film as grown. During the growth
of the thick porous film, spontaneous current oscillations have been observed. The frequency of oscillation was found to be
proportional to the current density, regardless of whether the measurements were carried out during a potential sweep or at
constant potential. Thus, the charge passed per oscillation remained constant. A characteristic value of approximately 0.3 C · cm−2 was measured under potential sweep conditions, and a similar value was obtained at constant potential.
Received October 16, 2001. Accepted (revised) December 21, 2001 相似文献
996.
Leroi C Bertin D Dufils PE Gigmes D Marque S Tordo P Couturier JL Guerret O Ciufolini MA 《Organic letters》2003,5(26):4943-4945
Thermolysis of alpha-alkoxyamino propionanilides produces indolinones, whereas thermal reaction of N-allylaniline derivatives with various Tordo-type alkoxyamines results in formation of indolines in the radical regime. [reaction: see text] 相似文献
997.
Guenelle Hari Andr Samat Robert Guglielmetti Inge van Parys Wim Saeyens Denis de Keukeleire Klaus Lorenz Albrecht Mannschreck 《Helvetica chimica acta》1997,80(4):1122-1132
The ease of thermal breaking of the C(sp3)? O bond of the 2-aryl-2-methyl-2H-1-benzopyrans 1 – 9 was evaluated by measuring the free energy (ΔG) of the racemization reaction of optically active compounds. The variation of ΔG of the thermal ring opening in terms of structural modifications is discussed. The synthesis of the studied compounds, the preparative separation of enantiomers by liquid chromatography, the determination of enantiomeric purity, the circular dichroism of enriched enantiomers, and the measurement of rate constants of enantiomerization by monitoring the decrease of the polarimetric angle of rotation at suitable temperatures are described. 相似文献
998.
Uzdensky A Bragin D Kolosov M Dergacheva O Fedorenko G Zhavoronkova A 《Photochemistry and photobiology》2002,76(4):431-437
To study the mechanism of photodynamic nerve cell killing, isolated crayfish mechanoreceptor neurons were photosensitized by the sulfonated aluminum ophthalocyanine Photosens. Neuron activity was continuously recorded until irreversible abolition. Intense (10(-5) M Photosens) or weak (10(-7) M Photosens) photosensitization induced different bioelectric neuron responses: firing activation followed by irreversible depolarization block or gradual inhibition until firing abolition, respectively. These bioelectric responses were accompanied by different biochemical and morphological changes. In the case of intense photosensitization, neuron nuclei swelled and then shrank. Succinate dehydrogenase (SDH) was inhibited, and the plasma membrane was compromised just after firing cessation. Weak photosensitization did not induce these changes but caused swelling of the endoplasmic reticulum and destruction of the matrix, cristae and membranes in some of the mitochondria. Other mitochondria, however, retained the normal structure. Plasma membrane damage, SDH inhibition, nucleus shrinkage and impairment of the nuclear border occurred after 2-4 h. It is concluded that intense photosensitization induced necrotic processes during irradiation, whereas weaker impact caused delayed necrosis 2-4 h later. The observed electrophysiological neuron responses to photodynamic therapy may be considered as early hallmarks of different modes of forthcoming cell death. 相似文献
999.
A new experimental approach based on the combination of calorimetric and FTIR spectroscopic measurements was proposed to study simultaneously the sorption of water and organic solvent, and corresponding changes in the structure of protein films in the water activity range from 0 to 1.0. Enthalpy changes (ΔHtot) on the interaction of water with the dried human serum albumin (HSA) in the presence and absence of acetonitrile (AN) have been measured using a Setaram BT-2.15 calorimeter at 298 K. Spectroscopic data on water and organic solvent vapor sorption by the HSA films and the corresponding changes in the protein secondary structure were determined by means of a Bruker Vector-22 FTIR spectrometer. By using a water activity-based comparison we characterised the effect of acetonitrile on the hydration and structure of the HSA films. Acetonitrile (AN) sorption isotherm resembles a smooth curve. HSA film binds about 250 mol AN/mol protein at the lowest water activities. As the water activity increases from 0 to 0.8, the sorption of AN gradually decreases from 250 to 150 mol AN/mol HSA. At aw > 0.8, the sorption of AN sharply decreases to zero. Acetonitrile decreases markedly the water content at a given aw. This behavior suggests that the suppression in the uptake of water is due to a competition for water-binding sites on the HSA films by acetonitrile. Changes in the secondary structure of HSA were determined from infrared spectra by analyzing the structure of amide I band. Acetonitrile increases the intensity of the 1654 cm−1 band that was assigned to the α-helix structure. Changes in the intensity of the 1654 cm−1 band agree well with the decrease in water uptake in the presence of AN. An explanation of the acetonitrile effect on the hydration and structure of the HSA films was provided on the basis of hypothesis on water-assisted disruption of polar contacts in the initially dried protein. 相似文献
1000.
The partial substitution of Co by Rh in the [Pb0⋅7Co0.4Sr1.9O3]RS[CoO2]1.8 family has been investigated. By transmission electron microscopy and X-ray powder diffraction, it is shown that the substitution of Rh for Co takes place at the two cobalt sites of the structure but for the low enough Rh contents, this substitution is made preferentially at the level of the CdI2-like layer. Thus, a generic formula [Pb0.7(Co0.4−zRhz)Sr1.9O3]RS[Co1−yRhyO2]b1/b2 (0?y?0.5 and 0?z?0.3) can be proposed for this new family of misfit phase. As observed for the pure misfit cobaltite, the thermoelectric power is also very large, close to +140 μV/K at room temperature. The Rh cation can adopt a mixed valency Rh3+/Rh4+ (4d6/4d5) with low spin states t2g6/t2g5 equivalent to the ones of low spin Co3+/Co4+ (3d6/3d5). The large thermopower observed in the Rh substituted compounds is therefore a direct proof that the coexistence of low spin states t2g6/t2g5 contributes to the thermoelectric power enhancement in these oxides. 相似文献