Search results for "molecular"
showing 10 items of 32340 documents
Selective Formation of S4- and T-Symmetric Supramolecular Tetrahedral Cages and Helicates in Polar Media Assembled via Cooperative Action of Coordina…
2020
We report on the synthesis and self-assembly study of novel supramolecular monomers encompassing quadruple hydrogen-bonding motifs and metal coordinating 2,2’-bipyridine units. When mixed with metal ions such as Fe2+ or Zn2+, the tetrahedron cage complexes are formed in quantitative yields and full diastereoselectivity, even in highly polar acetonitrile or methanol solvents. The symmetry of the complexes obtained has been shown to depend critically on the flexibility of the ligand. Restriction of the rotation of the hydrogen-bonding unit with respect to the metal coordinating site results in a T-symmetric cage, whereas by introducing flexibility either through a methylene linker or rotating…
The Hexameric Resorcinarene Capsule as a Brønsted Acid Catalyst for the Synthesis of Bis(heteroaryl)methanes in a Nanoconfined Space
2019
Herein, we show that the hexameric resorcinarene capsule C is able to catalyze the formation of bis(heteroaryl)methanes by reaction between pyrroles or indoles and carbonyl compounds (α-ketoesters or aldehydes) in excellent yields and selectivity. Our results suggest that the capsule can play a double catalytic role as a H-bond catalyst, for the initial activation of the carbonyl substrate, and as a Bronsted acid catalyst, for the dehydration of the intermediate alcohol.
Supramolecular Organocatalysis in Water Mediated by Macrocyclic Compounds
2018
In the last decades many efforts have been devoted to design supramolecular organocatalysts able to work in water as the reaction medium. The use of water as solvent provides promising benefits with respect to environmental impact. In this context, macrocyclic compounds played a role of primary importance thanks to their ease of synthesis and their molecular recognition abilities toward the reactants. The aim of this review is to give an overview of the recent advances in the field of supramolecular organocatalysis in water, focusing the attention on calixarene and cyclodextrins derivatives. Calixarenes and cyclodextrins, thanks to their hydrophobic cavities, are able to host selectively th…
Liquid Structure Scenario of the Archetypal Supramolecular Deep Eutectic Solvent: Heptakis(2,6-di-O-methyl)-β-cyclodextrin/levulinic Acid
2023
The concept of supramolecular solvents has been recently introduced, and the extended liquid-state window accessible for mixtures of functionalized cyclodextrins (CDs) with hydrogen bond (HB) donor species, e.g., levulinic acid, led to the debut of supramolecular deep eutectic solvents (SUPRA-DES). These solvents retain CD’s inclusion ability and complement it with enhanced solvation effectiveness due to an extended HB network. However, so far, these promising features were not rationalized in terms of a microscopic description, thus hindering a more complete capitalization. This is the first joint experimental and computational study on the archetypal SUPRA-DES: heptakis- (2,6-di-O-methyl)…
Influencing the self‐sorting behavior of [2.2]paracyclophane based ligands by introducing isostructural binding motifs
2020
Two isostructural ligands with either nitrile ( L nit ) or isonitrile ( L iso ) moieties directly connected to a [2.2]paracyclophane backbone with pseudo‐meta substitution pattern have been synthesized. The ligand itself ( L nit ) or its precursors ( L iso ) were resolved via HPLC on a chiral stationary phase and the absolute configuration of the isolated enantiomers was assigned by XRD analysis and/or by comparison of quantum‐chemical simulated and experimental ECD‐spectra. Surprisingly, the resulting metallosupramolecular aggregates formed in solution upon coordination of [(dppp)Pd(OTf) 2 ] differ in their composition: whereas L nit forms dinuclear complexes L iso exclusively forms trinuc…
Engineered surface waves in hyperbolic metamaterials
2013
We analyzed surface-wave propagation that takes place at the boundary between a semi-infinite dielectric and a multilayered metamaterial, the latter with indefinite permittivity and cut normally to the layers. Known hyperbolization of the dispersion curve is discussed within distinct spectral regimes, including the role of the surrounding material. Hybridization of surface waves enable tighter confinement near the interface in comparison with pure-TM surface-plasmon polaritons. We demonstrate that the effective-medium approach deviates severely in practical implementations. By using the finite-element method, we predict the existence of long-range oblique surface waves. This research was fu…
Molecular analysis of lichen-associated bacterial communities.
2006
The bacterial communities associated with 11 different lichen samples (belonging to eight different species) from different habitats were investigated. The culturable aerobic-heterotrophic fraction of the bacterial communities was isolated from nine lichen samples on protein-rich and sugar-rich/N-free media. Thirty-four bacterial isolates were purified and pooled into groups (phylotypes) by analysis of the ribosomal internal transcribed spacer polymorphism. Twenty five phylotypes were identified, each comprising between one and three isolates. One isolate of each phylotype was partially sequenced and the resulting 16S rRNA gene sequences were compared in a phylogenetic analysis. Three gener…
Theoretical and Experimental Study of Polarization Modulation Instability in All-Normal Dispersion Photonic Crystal Fibers
2018
Experimental observation of polarization modulation instability in all-normal dispersion photonic crystal fibers is reported. Stokes and anti-Stokes sidebands with spectral shift of 40 nm were observed when the fiber was pumped at 1064 nm. Experimental results are baked by a vectorial four-wave mixing model.
Theoretical investigation of the electronic structure of fullerenes
1994
Summary form only given. Research in the growing family of fullerene compounds are in continuous expansion. Much theoretical and experimental effort has been devoted to the study of the electronic properties these carbon cages present. However, although significant work has been done, the purpose of this paper is to provide a detailed theoretical analysis of the electronic properties of several fullerenes. We have calculated the electronic structure of these carbon cages within the valence effective Hamiltonian (VEH) approach. The calculated one-electron energy levels are correlated with experimental UPS spectra. The good correlation between calculated and experimental values shows VEH appr…
High Resolution Coherent Raman Spectroscopy: Studies of Molecular Structures
1992
One of the main advantages of the non-linear coherent Raman techniques is the high resolution that can be achieved in rovibrational spectroscopy. Typically an instrumental function of the order of several thousandths of a wavenumber is routinely achieved in SRS or CARS experiments. Since the first recording of the stimulated Raman spectrum of 12CH4 in 1978 [1], numerous studies of molecules have been performed [2–8]. We have built a stimulated Raman experiment in Dijon in which particular attention has been paid to the frequency measurement of the Raman lines [9]. We will describe the application of our experiment to a wide variety of molecules over the last few years: linear molecules, sph…