Search results for "chiral"
showing 10 items of 752 documents
Simulations on the mechanism of CNT bundle growth upon smooth and nanostructured Ni as well as θ-Al2O3 catalysts
2011
Abstract In the current study, we have performed ab initio DFT calculations on the gradually growing 2D periodic models of capped single-wall carbon nanotubes (SW CNTs) upon their perpendicular junctions with the Ni(111) substrate, in order to understand the peculiarities of the initial stage of their growth on either smooth or nanostructured catalytic particles. Appearance of the adsorbed carbon atoms upon the substrate follows from the dissociation of CVD hydrocarbon molecules, e.g., CH4: (CH4)ads → (CH)ads+3Hads and (CH)ads → Cads+Hads. (Since the effective growth of CNTs upon Ni nanoparticles occur inside the nanopores of amorphous alumina, we have also simulated analogous surface react…
Polycationic Monomeric and Homodimeric Asymmetric Monomethine Cyanine Dyes with Hydroxypropyl Functionality—Strong Affinity Nucleic Acids Binders
2021
New analogs of the commercial asymmetric monomethine cyanine dyes thiazole orange (TO) and thiazole orange homodimer (TOTO) with hydroxypropyl functionality were synthesized and their properties in the presence of different nucleic acids were studied. The novel compounds showed strong, micromolar and submicromolar affinities to all examined DNA ds-polynucleotides and poly rA–poly rU. The compounds studied showed selectivity towards GC-DNA base pairs over AT-DNA, which included both binding affinity and a strong fluorescence response. CD titrations showed aggregation along the polynucleotide with well-defined supramolecular chirality. The single dipyridinium-bridged dimer showed intercalatio…
Asymmetric Synthesis of Chiral Bimetallic [Ag28Cu12(SR)24]4– Nanoclusters via Ion Pairing
2016
In this work, a facile ion-pairing strategy for asymmetric synthesis of optically active negatively charged chiral metal nanoparticles using chiral ammonium cations is demonstrated. A new thiolated chiral three-concentric-shell cluster, [Ag28Cu12(SR)24]4–, was first synthesized as a racemic mixture and characterized by single-crystal X-ray structure determination. Mass spectrometric measurements revealed relatively strong ion-pairing interactions between the anionic nanocluster and ammonium cations. Inspired by this observation, the as-prepared racemic mixture was separated into enantiomers by employing chiral quaternary ammonium salts as chiral resolution agents. Subsequently, direct asymm…
Kaon-proton strong interaction at low relative momentum via femtoscopy in Pb-Pb collisions at the LHC
2021
Physics letters / B 822, 136708 (2021). doi:10.1016/j.physletb.2021.136708
Two new metabolites from the endophytic fungus Xylaria sp. isolated from the medicinal plant Curcuma xanthorrhiza
2015
Abstract The endophytic fungus Xylaria sp. was isolated from healthy leaves of Curcuma xanthorrhiza, collected on the island of Timor, Indonesia. Two new compounds (1 and 2), together with the known resacetophenone (3), were isolated and their structures were elucidated on the basis of comprehensive NMR and mass spectral analyses. The enantiomers of rac-1 were separated by chiral HPLC and their HPLC-ECD spectra were recorded to determine the absolute configuration on the basis of TDDFT-ECD calculations. The (3R,3aR, 9aR) absolute configuration of the optically active 2 was established by comparing the experimental solution ECD spectrum with the TDDFT ones computed for the gas phase and solu…
Precise branching ratios to unbound 12C states from 12N and 12B β-decays
2009
6 pages, 2 tables, 4 figures.--PACS nrs.: 21.45.-v; 23.40.-s; 27.20.+n; 21.60.De.--Printed version published Aug 3, 2009
A general diastereoselective synthesis of highly functionalized ferrocenyl ambiphiles enabled on a large scale by electrochemical purification
2017
International audience; A general synthesis of highly functionalized ferrocenes, which include (P,B)- and (N,B)-ambiphiles, has been developed at a multigram scale. Diastereoselective stepwise modification of di-tert-butylated ferrocenes included the unprecedented separation of electroactive species. Bulky alkyl groups on ferrocenes ensure planar chirality of ambiphiles and enforce closer proximity of antagonist Lewis functions.
Synthesis of Optically Active Hydroxyalkyl Cycloheptatrienes: A Key Step in the Total Synthesis of 6,11-Methylene-LXB4
2020
AbstractStarting from methyl cycloheptatrienyl-1-carboxylate, 6-acylation was successfully achieved employing glutaryl chloride in the presence of AlCl3 under controlled reaction conditions to furnish keto carboxylic acid product. After protection of this keto carboxylic acid as tert-butyl ester, reagent-controlled enantioselective reductions delivered configuration-defined methyl-6-hydroxylalkyl cycloheptatriene-1-carboxylates with up to 80% ee. Whereas simple NaBH4 reduction of the keto carboxylic acid and subsequent lactonization afforded a methyl-6-tetrahydropyranonyl cycloheptatriene-1-carboxylate. Resolution using chiral HPLC delivered the product enantiomers with up to >99% ee Fin…
Recent Developments in the Chiral Brønsted Acid-catalyzed Allylboration Reaction with Polyfunctionalized Substrates
2016
Asymmetric allylboration has played a central role in organic synthesis ever since the pioneering work by Hoffman and Brown, having found applications in the total synthesis of many natural products. A new dawn for this 40 year-old reaction occurred with the beginning of the new century when the first catalytic asymmetric methods came into play. In less than one decade, several methodologies, able to achieve the desired homoallylic alcohols with ee ranges in the high 90s, were developed. Among them, in the present account, we will disclose our contribution to the development of the chiral binolphosphoric-derived BrOnsted acid-catalyzed allylboration of aldehydes originally reported by Antil…
Enantiodivergent synthesis of P-chirogenic phosphines
2010
International audience; Several approaches for the enantiodivergent synthesis of P-chirogenic mono- and diphosphines are described, using ephedrine methodology and phosphine borane chemistry. Firstly, both enantiomers of a tertiary phosphine can be obtained starting from the same oxazaphospholidine borane complex, prepared from (+)-ephedrine, when changing the order of addition of the organolithium reagents during the synthetic pathway. The second approach is based on the chlorophosphine boranes, which react with an organolithium reagent, to afford the corresponding phosphines with inversion of configuration. In the case where the chlorophosphine borane reacts with the t-butyl lithium reage…