Phenyl α-bromovinyl sulfone reacts with glycine ester Schiff bases regioselectively in the presence of catalytic amounts of AgOAc and DBU yielding polysubstituted pyrrolidine cycloadducts. Utilization of excess DBU induces subsequent facile aromatization of the cycloadducts and affords 5-arylpyrrole-2-carboxylic acid esters in 39-85% yields in a single step. 相似文献
The first direct synthesis of 3-N-methyl-9-formylcytisine via electrophylic formylation is described. It is established, that Vilsmeier-Haack and Gatterman variants of this reaction are unsuccessful in the case with 3-substituted (-)-cytisine derivatives, but Duff procedure (with hexamethylenetetramine in trifluoroacetic acid) gives a possibility to obtain the target pseudo aromatic aldehyde with the 69% yield. Convenient precursors for [4 + 2]- or [3 + 2]-cycloaddition reactions are obtained by means of condensation of synthesized 3-N-methyl-9-formylcytisine with acetone, nitromethane and phosphorous ylides with yields from 70 to 87%. Alternative aprroach to alkenyl products and to 9-alkynyl-3-methylcytisine is realized using the Heck and Sonogashira cross-coupling reactions of methyl vinyl ketone, cyclohexenone or trimethylsilylacetylene with 9-bromo-3-methylcytisine (55, 70 and 60% accordingly). It is shown, that interaction of 3-N-methyl-9-formylcytisine with hydroxylamines leads to corresponding nitrone (93%) and oxime (70%). All individual compounds are isolated by column chromatography and completely characterized on the basis of NMR spectroscopy data. 相似文献
Preclassification of raw infrared spectra has often been neglected in scientific literature. Separating spectra of low spectral quality, due to low signal-to-noise ratio, presence of artifacts, and low analyte presence, is crucial for accurate model development. Furthermore, it is very important for sparse data, where it becomes challenging to visually inspect spectra of different natures. Hence, a preclassification approach to separate infrared spectra for sparse data is needed. In this study, we propose a preclassification approach based on Multiplicative Signal Correction (MSC). The MSC approach was applied on human and the bovine knee cartilage broadband Fourier Transform Infrared (FTIR) spectra and on a sparse data subset comprising of only seven wavelengths. The goal of the preclassification was to separate spectra with analyte-rich signals (i.e., cartilage) from spectra with analyte-poor (and high-matrix) signals (i.e., water). The human datasets 1 and 2 contained 814 and 815 spectra, while the bovine dataset contained 396 spectra. A pure water spectrum was used as a reference spectrum in the MSC approach. A threshold for the root mean square error () was used to separate cartilage from water spectra for broadband and the sparse spectral data. Additionally, standard noise-to-ratio and principle component analysis were applied on broadband spectra. The fully automated MSC preclassification approach, using water as reference spectrum, performed as well as the manual visual inspection. Moreover, it enabled not only separation of cartilage from water spectra in broadband spectral datasets, but also in sparse datasets where manual visual inspection cannot be applied. 相似文献
We present a new experiment demonstrating destructive interference in customers’ estimates of conditional probabilities of product failure. We take the perspective of a manufacturer of consumer products and consider two situations of cause and effect. Whereas, individually, the effect of the causes is similar, it is observed that when combined, the two causes produce the opposite effect. Such negative interference of two or more product features may be exploited for better modeling of the cognitive processes taking place in customers’ minds. Doing so can enhance the likelihood that a manufacturer will be able to design a better product, or a feature within it. Quantum probability has been used to explain some commonly observed “non-classical” effects, such as the disjunction effect, question order effect, violation of the sure-thing principle, and the Machina and Ellsberg paradoxes. In this work, we present results from a survey on the impact of multiple observed symptoms on the drivability of a vehicle. The symptoms are assumed to be conditionally independent. We demonstrate that the response statistics cannot be directly explained using classical probability, but quantum formulation easily models it, as it allows for both positive and negative “interference” between events. Since quantum formalism also accounts for classical probability’s predictions, it serves as a richer paradigm for modeling decision making behavior in engineering design and behavioral economics. 相似文献
The study of the molecular mechanisms of the pathogenesis of Alzheimer’s disease (AD) is extremely important for identifying potential therapeutic targets as well as early markers. In this regard, the study of the role of post-translational modifications (PTMs) of β-amyloid (Aβ) peptides is of particular relevance. Serine-8 phosphorylated forms (pSer8-Aβ) have been shown to have an increased aggregation capacity and may reflect the severity of amyloidosis. Here, an approach for quantitative assessment of pSer8-Aβ based on matrix-assisted laser desorption/ionization time-of-flight mass spectrometry (MALDI-TOF MS) is proposed. The relative fraction of pSer8-Aβ was estimated in the total Aβ-pool with a detection limit of 1 fmol for pSer8-Aβ (1–16) and an accuracy of 2% for measurements in the reflectron mode. The sensitivity of the developed method is suitable for determining the proportion of phosphorylated peptides in biological samples. 相似文献
Sols of core–shell silver nanoparticles (AgNPs) are synthesized by electrochemical method. The method provides the ability to adjust the particle size by changing both the concentration of oleic acid and the residence time τ0 in the organic phase. We synthesized AgNPs with oleic acid (OA) concentration of 0.25% (AgNPs & 0.25% OA) and 0.75% (AgNPs & 0.75% OA). These nanoparticles have been studied using modern physical–chemical methods. Differential thermal analysis curves indicate the chemical nature of bond ligand in the secondary shell; this conclusion is confirmed by quantum chemical simulation and semi-empirical calculation. In the electron paramagnetic resonance spectra of silver-containing sols AgNPs & 0.25% OA and AgNPs & 0.75% OA complex wide asymmetric signals of 500–800 G and g-factor of 2.09–2.13 are recorded, in addition, in the spectra of AgNPs with bilayer the pronounced ferromagnetic contribution is observed. The change of the oleic acid layers of the particles affects the dimension of the nanocrystallites that are being formed and the manifestation of their magnetism.
Trial registration number and date of registration JCS-P-20-03-0188.R1, 22-Sep-2020 (02-Mar-2020)
The uracil analog, 4-fluoro-2-pyridone was synthesized by ether cleavage of 4-fluoro-2-methoxypyridine with trimethylsilyl iodide. Improved procedures for the preparations of 2-methoxypyridine N-oxide hydrochloride and 2-methoxy-4-nitropyridine N-oxide are described. 相似文献