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101.
Chaimae Bariki Fabien Halter Fabien Thiesset Christian Chauveau Iskender Gökalp Ketana Teav Sina Kheirkhah Adam M. Steinberg 《Proceedings of the Combustion Institute》2019,37(2):1911-1918
Simultaneous measurements of temperature, CH* and OH* chemiluminescent species are carried out to explore the impact of stretch rate and curvature on the structure of premixed flames. The configuration of an initially flat premixed flame interacting with a toroidal vortex is selected for the present study and reasons for this choice are discussed. Lewis number effects are assessed by comparing methane and propane flames. It is emphasized that the flame structure experiences very strong variations. In particular, the flame is shrunk (broadened) in the initial (final) period of the interaction with the vortex where strain rate (curvature) contribution of the stretch rate is predominant. By further analysing independently the thickness of the preheat and reaction zones, it is shown that for propane flames, not only the former but also the latter is significantly altered in zones where the flame curvature is negative. Changes in the reaction zone properties are further emphasized using CH* and OH* radicals. It is demonstrated that higher thermal diffusivity plays a significant role around curved regions, in which the enhanced diffusion of heat leads to a strong increase of CH* compared to OH* intensity. As an overall conclusion, this study suggests that it would be interesting to reassess the internal flame structure at lower and moderate Karlovitz numbers since changes might appear for a moderate vortex intensity with typical size much larger than the flame thickness. 相似文献
102.
Rondahl Stina Holmgren Pointurier Fabien Ahlinder Linnea Ramebäck Henrik Marie Olivier Ravat Brice Delaunay François Young Emma Blagojevic Ned Hester James R. Thorogood Gordon Nelwamondo Aubrey N. Ntsoane Tshepo P. Roberts Sarah K. Holliday Kiel S. 《Journal of Radioanalytical and Nuclear Chemistry》2018,315(2):395-408
Journal of Radioanalytical and Nuclear Chemistry - This work presents the results for identification of chemical phases obtained by several laboratories as a part of an international nuclear... 相似文献
103.
Antoine Versini Lou Saier Fabien Sindikubwabo Sebastian Müller Tatiana Cañeque Raphaël Rodriguez 《Tetrahedron》2018,74(39):5585-5614
Cancer stem cells (CSC) have been shown to be refractory to conventional therapeutic agents, can promote metastasis, and have been linked to cancer relapse. The natural product Salinomycin has been identified by means of high throughput phenotypic screening as a selective killer of CSC in vitro and in vivo. In this article we comprehensively review the chemistry of Salinomycin, documenting early total syntheses, along with strategies that have been developed over the years to effectively modify this natural product at key positions with the view to establish a robust structure-activity-relationship and to delineate the complex mechanism of action of this fascinating molecule in the context of cancer research. Then, we document the biology of Salinomycin, putting forward phenotypic alterations that have been observed in the relevant biological models and highlighting how chemistry has been instrumental in discovering unprecedented physiological features of cancer stem cells that can be exploited for therapeutic benefits. 相似文献
104.
Tatiana Cañeque Sebastian Müller Anne Lafon Fabien Sindikubwabo Antoine Versini Lou Saier Manon Barutaut Christine Gaillet Raphaël Rodriguez 《Comptes Rendus Chimie》2018,21(7):704-708
Cancer stem cells (CSCs) have been shown to be refractory to conventional therapeutic agents, can promote metastasis, and have been linked to cancer relapse. Salinomycin can selectively kill CSCs. We have shown that salinomycin derivatives accumulate in lysosomes and sequester iron in this organelle. As a result, accumulation of iron leads to the production of reactive oxygen species and lysosomal membrane permeabilization, which in turn promotes cell death by ferroptosis. These findings have revealed the prevalence of iron homeostasis in CSCs and paved the way toward the development of next-generation therapeutics. 相似文献
105.
106.
Fabien Pascale Klaus Doll Francesco Silvio Gentile Roberto Dovesi 《Journal of computational chemistry》2023,44(2):65-75
The ferromagnetic and antiferromagnetic wave functions of the KMnF3 perovskite have been evaluated quantum-mechanically by using an all electron approach and, for comparison, pseudopotentials on the transition metal and the fluorine ions. It is shown that the different number of α and β electrons in the d shell of Mn perturbs the inner shells, with shifts between the α and β eigenvalues that can be as large as 6 eV for the 3s level, and is far from negligible also for the 2s and 2p states. The valence electrons of F are polarized by the majority spin electrons of Mn, and in turn, spin polarize their 1s electrons. When a pseudopotential is used, such a spin polarization of the core functions of Mn and F can obviously not take place. The importance of such a spin polarization can be appreciated by comparing (i) the spin density at the Mn and F nuclear position, and then the Fermi contact constant, a crucial quantity for the hyperfine coupling, and (ii) the ferromagnetic–antiferromagnetic energy difference, when obtained with an all electron or a pseudopotential scheme, and exploring how the latter varies with pressure. This difference is as large as 50% of the all electron datum, and is mainly due to the rigid treatment of the F ion core. The effect of five different functionals on the core spin polarization is documented. 相似文献
107.
Dr. David F. León Rayo Ali Mansour Dr. Wenbin Wu Dr. Benjamin N. Bhawal Prof. Fabien Gagosz 《Angewandte Chemie (International ed. in English)》2023,62(3):e202212893
Direct C−H bond functionalization is a useful strategy for the straightforward formation of C−C and C−Heteroatom bonds. In the present work, a unique approach for the challenging electrophilic Au-catalyzed α-C−H bond functionalization of tertiary amines is presented. Electronic, steric and conformational synergistic effects exerted by the use of a malonate unit in the substrate were key to the success of this transformation. This new reactivity was applied to the synthesis of tetrahydro-γ-carboline products which, under oxidative conditions, could be converted into valuable structural motifs found in bioactive alkaloid natural products. 相似文献
108.
Koch R Finnerty JJ Bruhn T Borget F Wentrup C 《The journal of physical chemistry. A》2008,112(38):8999-9004
The complex reaction of thermally generated iminopropadienones with amines in the gas phase and upon matrix deposition and its varying product composition is investigated using density functional theory. In the high energy gas phase addition a single amine molecule reacts readily with iminopropadienone with the decisive step being a 1,3-hydrogen shift and activation barriers of at least 100 kJ/mol. In accordance with the experiment, the formation of ketenes is favored. In the condensed phase of an amine matrix, the utilization of amine dimers both as reagents and as explicit solvents lowers the activation energy required to a feasible 20-30 kJ/mol and predicts ketenimines as the main products, as observed experimentally. 相似文献
109.
Silly F Shaw AQ Castell MR Briggs GA 《Chemical communications (Cambridge, England)》2008,(16):1907-1909
The mixing of perylene-3,4,9,10-tetracarboxylic diimide (PTCDI) and 1,3,5-triazine-2,4,6-triamine (melamine) at room temperature in a ratio of 3 : 4 on Au(111) leads to the formation of a new chiral "pinwheel" structure. 相似文献
110.
Samuel F. Cousin Dr. Pavel Kadeřávek Baptiste Haddou Dr. Cyril Charlier Thorsten Marquardsen Jean‐Max Tyburn Dr. Pierre‐Alain Bovier Dr. Frank Engelke Dr. Werner Maas Prof. Dr. Geoffrey Bodenhausen Dr. Philippe Pelupessy Prof. Dr. Fabien Ferrage 《Angewandte Chemie (International ed. in English)》2016,55(34):9886-9889
Nuclear magnetic resonance (NMR) studies have benefited tremendously from the steady increase in the strength of magnetic fields. Spectacular improvements in both sensitivity and resolution have enabled the investigation of molecular systems of rising complexity. At very high fields, this progress may be jeopardized by line broadening, which is due to chemical exchange or relaxation by chemical shift anisotropy. In this work, we introduce a two‐field NMR spectrometer designed for both excitation and observation of nuclear spins in two distinct magnetic fields in a single experiment. NMR spectra of several small molecules as well as a protein were obtained, with two dimensions acquired at vastly different magnetic fields. Resonances of exchanging groups that are broadened beyond recognition at high field can be sharpened to narrow peaks in the low‐field dimension. Two‐field NMR spectroscopy enables the measurement of chemical shifts at optimal fields and the study of molecular systems that suffer from internal dynamics, and opens new avenues for NMR spectroscopy at very high magnetic fields. 相似文献