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Mukaiyama–Michael Reactions with trans‐2,5‐Diarylpyrrolidine Catalysts: Enantioselectivity Arises from Attractive Noncovalent Interactions,Not from Steric Hindrance 下载免费PDF全文
Dr. Eeva K. Kemppainen Dr. Gokarneswar Sahoo Antti Piisola Andrea Hamza Bianka Kótai Dr. Imre Pápai Prof. Petri M. Pihko 《Chemistry (Weinheim an der Bergstrasse, Germany)》2014,20(20):5983-5993
The scope of the enantioselective Mukaiyama–Michael reactions catalyzed by trans‐2,5‐diphenylpyrrolidine has been expanded to include both α‐ and β‐substituted enals. However, the rationalization of the observed enantioselectivity is far from obvious since the catalyst is not very sterically hindered. DFT calculations were carried out to rationalize the observed stereoselectivities. Transition states of the C?C bond formation between iminium intermediates and silyloxyfurans were located and their relative energies were used to estimate the stereoselectivity data. We find excellent agreement between the predicted and observed stereoselectivities. The analysis of intermolecular forces reveals that the enantioselectivity is mostly due to stabilizing noncovalent interactions between the reacting partners, not due to steric hindrance. The role of attractive noncovalent interactions in enantioselective catalysis may be underappreciated. 相似文献
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7‐(2‐Oxoalkoxy)coumarins: Synthesis and Anti‐Inflammatory Activity of a Series of Substituted Coumarins 下载免费PDF全文
Juri Timonen Katriina Vuolteenaho Tiina Leppänen Riina Nieminen Eeva Moilanen Paula Aulaskari Janne Jänis 《Journal of heterocyclic chemistry》2015,52(5):1286-1295
A series of 7‐(2‐oxoalkoxy)coumarins have been synthesized by conjugating substituted 7‐hydroxycoumarins with different chloroketones. The anti‐inflammatory properties of 7‐(2‐oxoalkoxy)coumarins were studied in LPS‐induced inflammatory response in J774 macrophages. Western blot was used to determine the expression of iNOS and COX‐2, NO was determined by measuring its metabolite nitrite by Griess reaction and IL‐6 was measured by ELISA. Seventeen of the studied compounds inhibited NO and IL‐6 production over 50% at 100 μM concentrations. IC50 values of the best inhibitors were 21 μM/24 μM (NO/IL‐6) for compound 12 and 30 μM/10 μM (NO/IL‐6) for compound 20 . The main result was that the substitution with 7‐(2‐oxoalkoxy) group improved the anti‐inflammatory properties of most of the investigated 7‐hydroxycoumarins. 相似文献
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The present article describes a capillary zone electrophoresis method which relies on a multilayered water-alkali solvent stacking with online ionization to enhance detection of mannose, arabinose, and their oligosaccharides, which are used as the migration profile standards but are also the distinctive structural components of lipoarabinomannan. Lipoarabinomannan is detected in patients having tuberculosis. The capillary electrophoresis method with ionization of the whole saccharides without degradation in alkaline solution inside the capillary is based on the structural deprotonation of the molecules under ultrahigh pH conditions. The validation of the capillary electrophoresis parameters revealed that the 15-fold electrolyte–water-injection plug allowed detection of one-third lower concentrations than detected without online concentration. For the first time, the better detectability was seen especially for highly polymerized, but otherwise poorly ionized, arabinooctaose. The applicability of the method for detecting whole large biological saccharide complexes was confirmed by the glycolipid lipoarabinomannan. For the first time also, the migration of the indestructible lipoarabinomannan was detected together with oligosaccharides used representing the capping units, namely mannose, mannobiose, and mannotriose. The myo-inositol-phosphate-lipid unit was seen to migrate separately from the arabinomannan, since it was hydrolyzed from one lipoarabinomannan product under alkaline conditions in capillary electrophoresis. 相似文献
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In vitro degradation of porous 50/50, 70/30 and 90/10 PLGA (poly(dl-lactide-co-glycolide)) foams and PLGA/bioactive glass (20 wt%) composite foams was studied up to 16 weeks in TRIS (pH 7.4; 37 °C). Polar PLGA/bioactive glass composite films were prepared by applying the bioactive glass (S53P4) on one side of the composite. Porous foams were made by solvent casting and pressure quenching with CO2. The fabricated foams had an initial pore size of 50-500 μm and thickness of 2-2.5 mm. In vitro degradation of the prepared foams was evaluated after 1, 2, 4, 6, 8, 12 and 16 weeks. Weight loss, water uptake, molecular mass and the amount of dissolved bioactive glass were measured after each time period. Changes in pore morphology were analysed with SEM. The present in vitro results will be evaluated and compared with the results from ongoing animal studies where comparable implants are used for bone defect treatment under non-load-bearing conditions. 相似文献
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Eeva Heliövaara Henri Liljeqvist Dr. Mikko Muuronen Aleksi Eronen Karina Moslova Prof. Timo Repo 《Chemistry (Weinheim an der Bergstrasse, Germany)》2021,27(34):8668-8672
Development of new, environmentally benign dissolution methods for metallic gold is driven by needs in the circular economy. Gold is widely used in consumer electronics, but sustainable and selective dissolution methods for Au are scarce. Herein, we describe a quantitative dissolution of gold in organic solution under mild conditions by using hydrogen peroxide as an oxidant. In the dissolution reaction, two thiol ligands, pyridine-4-thiol and 2-mercaptobenzimidazole, work in a cooperative manner. The mechanistic investigations suggest that two pyridine-4-thiol molecules form a complex with Au0 that can be oxidized, whereas the role of inexpensive 2-mercaptobenzimidazole is to stabilize the formed AuI species through a ligand exchange process. Under optimized conditions, the reaction proceeds vigorously and gold dissolves quantitatively in two hours. The demonstrated ligand-exchange mechanism with two thiols allows to drastically reduce the thiol consumption and may lead to even more effective gold dissolution methods in the future. 相似文献
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Vocal symptoms and voice disorders among teachers were studied in 1988 using a questionnaire designed to obtain information on six vocal symptoms that had appeared during the past 2 years. Twelve percent of the 478 respondents reported vocal symptoms occurring weekly or more often. The study was repeated using the same questionnaire in 2001. The results of this second study (n=241) indicate that vocal symptoms had increased considerably. Twenty-nine percent of the teachers reported symptoms occurring weekly or more often, and 20% reported two symptoms or more occurring at least once a week, which is significantly more than in 1988. Accordingly, voice disorders are probably a growing problem among teachers. Several factors may explain these increases. In 2001, the teachers complained more often about increases in the size of their classes. Factors that disturbed normal work routines, such as noisy or misbehaving pupils, had also increased significantly. A growing number of misbehaving pupils probably cause increased background noise and stress and, thus, increase the vocal symptoms in teachers. 相似文献
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Studies focusing on different groups of students show that the prevalence of vocal symptoms and voice disorder vary depending on the study populations. A previous study of vocal symptoms and voice disorders among teacher students has shown that 20% of the students studying to become teachers in comprehensive schools and upper secondary schools reported frequently occurring vocal symptoms, ie, two symptoms or more occurring weekly or more often during the past year, and that most of these students had an organic voice disorder. This raised the question of whether other university students would also report similar, frequently occurring vocal symptoms. A questionnaire was distributed to 220 students of several faculties at the University of Turku, Finland. The results were compared with the results of a study of vocal symptoms reported by 175 students studying to become teachers. This comparison showed that students in general reported frequently occurring vocal symptoms, whereas the students studying to become teachers reported a greater number of frequently occurring symptoms than did other students at the university. 相似文献
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Erkki Vilkman Eija-Riitta Lauri Paavo Alku Eeva Sala Marketta Sihvo 《Journal of voice》1999,13(2):303-312
The effects of prolonged (5x45 minute) reading (vocal loading) on fundamental frequency (F0), sound pressure level (SPL), subglottal (intraroral) pressure (p), and two glottal flow waveform parameters (AC amplitude of glottal flow, f, and negative peak amplitude of differentiated flow (d) of normal female and male subjects (N = 80) were studied. Two rest (morning and noon) and three loading (two in the morning and one in the afternoon) samples were recorded and analyzed. The glottal waveforms were obtained by inverse filtering of the acoustic pressure waveforms of speaking voice samples. The analyses were based on measurement and inverse filtering of the first stressed syllable of "paappa" words repeated 3x5 times for normal, as soft as possible, and as loud as possible phonation. In normal phonation the parameter values changed statistically significantly due to loading. In many cases the values obtained in the morning samples changed after the first loading session. This is interpreted as a vocal "warming-up effect." Especially in soft phonation p, d, and f were sensitive indicators of vocal loading. In both normal and soft phonation, the SPL, p, d, and f values tended to rise due to prolonged reading in the morning and afternoon samples, indicating increased effort (normal phonation) and a rise in the phonatory threshold (soft phonation). The lunch break vocal rest ("rest effect") considerably affected the parameter values in many cases. 相似文献
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