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Abstract
Ferrocene- and ruthenocenecarboxaldehydes have been employed in Betti-type condensation reactions with 2-naphthol and (S)-phenylethylamine to give metallocenyl-substituted aminomethylnaphthols in a diastereoisomerically pure form. The absolute configurations of the new chiral compounds have been determined by means of NMR experiments and confirmed by X-ray crystallography. The chiral metallocenyl-aminomethylnaphthols have been tested as pre-catalysts for the addition of diethyl zinc to aldehydes, with enantioselectivities of up to 88% ee. (C) 2019 Elsevier Ltd. All rights reserved.
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Abstract
A straightforward approach to the synthesis of two different series of cationic [5]helicenes has been achieved including, in dioxa series, the possibility to introduce aromatic functional groups at the periphery of the helical structure. While photophysical study highlights that the introduction of aryl substituents at position 23 of the helical moieties has a negligible impact on the optical properties, styryl substituents allow a welcoming extension of the conjugation pathways. Finally, a red shift of the optical properties was evidenced upon introduction of nitrogen atoms in the helicene scaffold, leading to particularly good fluorescence efficiencies in the red domain for a helicenic dye. Detailed information on racemization kinetics was collected for the most stable species upon direct high-performance liquid chromatography (HPLC) resolution or, when configurational lability was too high, through VT-HPLC analysis on the chiral stationary phase (Delta G double dagger values ranging from 85.0 to 137.1 kJ.mol(-1) and above).
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Abstract
An entry from the Cambridge Structural Database, the worlds repository for small molecule crystal structures. The entry contains experimental data from a crystal diffraction study. The deposited dataset for this entry is freely available from the CCDC and typically includes 3D coordinates, cell parameters, space group, experimental conditions and quality measures.
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Abstract
The utility of deoxy-isoequilenine synthesized from estrone as valuable 2-naphthol analogue is demonstrated in the three components Betti-condensation. A simple, efficient and green procedure for the synthesis of aminobenzylnaphthol analogues (so-called Betti bases) has been realized highly diastereoselectively by using (S)-phenylethylamine and 1- or 2-naphthaldehyde. The absolute configuration of the new chiral compounds obtained has been determined by means of NMR experiments and confirmed by X-ray crystallography. The chiral steroidal aminobenzylnaphthols have been evaluated as pre-catalysts for the addition of diethylzinc to aldehydes with enantioselectivities of up to 98% ee.
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Abstract
Context. Stellar feedback is one of the fundamental factors regulating the evolution of galaxies. However, we still do not have access to strong observational constraints on the relative importance of the di fferent feedback mechanisms (e.g. radiation, ionised gas pressure, stellar winds) in driving H II region evolution and molecular cloud disruption. To quantify and compare the di fferent feedback mechanisms, the size of an H II region is crucial, whereas samples of well-resolved H II regions are scarce.
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Abstract
The chlorophyll a antenna of photosystems I and II were each isolated after detergent treatment by gel electrophoresis or sucrose gradient centrifugation from a b-less mutant of barley grown in daylight and from wildtype barley developed in intermittent light. We identified each fraction by both its electrophoretic position and PS I activity (P700 content) in the case of the mutant, and by both PS I and PS II activity (DCIP reduction from DPC) in the light-limited plants. The proportion of Chl a in each photosystem was estimated from the amount in each gel or sucrose gradient band, and from addition of the areas under the absorption spectra (650-710 nm) of each fraction to match the spectrum of the solubilized thylakoids. The latter method was possible because the spectrum (77 K) of each fraction was unique; in the mutant about 70% of chlorophyll is associated with PS I and 30% with PS II. In the light-limited plants, the reverse is true with nearly 70% associated with PS II. RESOL analyses of both absorption and fluorescence emission spectra of all isolated fractions indicated an abnormal arrangement of antenna chlorophyll molecules in the light-limited, developing membranes even though their reaction centers are fully functional.
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