Jean-Paul Cornard

The influence of the composition of the functional used for density functional theory computations on one structural parameter (a dihedral angle) and a spectroscopic parameter (absorption wavelength) is assessed in this study on the basis of two molecules (flavonols). In this kind of molecules, these two parameters should be correlated according to the nature of the electronic transition involved. However, it is shown herein that by varying the proportion of true exchange and correlation while building a functional, it is possible to obtain independently a large range of values for these parameters without any relation with the underlying real values. Therefore, it is concluded that the choice of a functional after a benchmark, especially using user-defined functionals, should be carried out with great care to avoid such effects.

2′,3-Dihydroxyflavone (2′3HF) is a natural flavonol that has barely ever been studied, however the scarce studies of its physico-chemical properties have highlighted its atypical behaviour. We present a structural and spectral study of 2′3HF, performed using UV-visible absorption and fluorescence spectroscopies, coupled with DFT and TD-DFT calculations. Although its structure is close to that of 3-hydroxyflavone, 2′3HF shows a much lower pK_a value. We show that the origin of this particularity is the substitution by a hydroxyl group on position 2′, that induces a stronger inter-ring interaction weakening the bonding of the proton at position 3. The main absorption band of the is red-shifted upon deprotonation. The remaining proton is highly bonded in between oxygen atoms 3 and 2′, making the second deprotonation unattainable in methanol. The neutral form can undergo an excited-state intramolecular proton transfer to emit dual fluorescence by the normal and tautomer forms. We suggested five geometries to be the sources of the emission bands, and showed that the energy barriers to interconversions were almost null. The anion is also fluorescent. The Stokes shifts for the neutral normal and anion species are extremely high, that can be explained by the conformational rearrangement, as the species go from twisted in the ground-state, to planar in the excited-state. Finally, another emission band is evidenced when exciting in the vicinity of the absorption maximum of the anion species in acidic medium. We suggest an aggregate with the solvent to be the origin of the emission.

After mixing HZSM-5 single crystals and solid t-stilbene, micro Raman mapping and micro fluorescence emission imaging provide evidence of the adsorption, spontaneous ionization and diffusion of the guest into the pores of zeolite. The experiments provide evidence of both radical cation and subsequent charge transfer complexes (CTC). Using a set of excitation wavelengths, Raman spectra of different charge separated states (CSS) were identified by taking advantage of the resonance effect; the correct assignment of the species stabilized in the single crystal is confirmed by analysis of the reference CSS stabilized in powder samples. This assignment is also supported by the correlation of fluorescence emission images obtained for single crystals at different excitation wavelengths and the fluorescence excitation–emission matrix (EEM) plots obtained for the powder reference samples. Thanks to complementary fluorescence and Raman imaging techniques, the spatial distribution of the CSS was found to be mainly located at the tips and in the intergrowth after long times of contact which are correlated with high loading rates. Unusual Al zoning at the crystal extremities and higher polarity in the sinusoidal pores might be put forward to explain these features.

Odorant-binding proteins (OBP) are secreted in the nasal mucus at the vicinity of olfactory receptors (ORs). They act, at least, as an interface between hydrophobic and volatile odorant molecules and the hydrophilic medium bathing the ORs. They have also been hypothesized to be part of the molecular coding of odors and pheromones, by forming specific complexes with odorant molecules that could ultimately stimulate ORs to trigger the olfactory transduction cascade. In a previous study, we have evidenced that pig olfactory secretome was composed of numerous olfactory binding protein isoforms, generated by O-GlcNAcylation and phosphorylation. In addition, we have shown that recombinant OBP (stricto sensu) produced in yeast is made up of a mixture of isoforms that differ in their phosphorylation pattern, which in turn determines binding specificity. Taking advantage of the high amount of OBP secreted by a single animal, we performed a similar study, under exactly the same experimental conditions, on native isoforms isolated from pig, Sus scrofa, nasal tissue. Four fractions were obtained by using strong anion exchange HPLC. Mapping of phosphorylation and O-GlcNAcylation sites by CID-nanoLC-MS/MS allowed unambiguous localization of phosphosites at S13 and T122 and HexNAc sites at S13 and S19. T112 or T115 could also be phosphorylated. BEMAD analysis suggested extra phosphosites located at S23, S24, S41, S49, S57, S67, and T71. Due to the very low stoichiometry of GlcNAc-peptides and phosphopeptides, these sites were identified on total mixture of OBP isoforms instead of HPLC-purified OBP isoforms. Nevertheless, binding properties of native OBP isoforms to specific ligands in S. scrofa were monitored by fluorescence spectroscopy. Recombinant phosphorylated OBP-Pichia isoforms bind steroids and fatty acids with slight differences. Native isoforms, that are phosphorylated but also O-GlcNAcylated show radically different binding affinities for the same compounds, which strongly suggests that O-GlcNAcylation increases the binding specificity of OBP isoforms. These findings extend the role of O-GlcNAc in regulating the function of proteins involved in many mechanisms of metabolic homeostasis, including extracellular signaling in olfaction. Data is available via ProteomeXChange with identifier PXD011371.

The current study aims at obtaining a better understanding of the mechanisms involved in the complexation of copper ions by 3-hydroxyflavone (3HF), which is one of the most studied compounds of the flavonoid family. To achieve this goal, quantum chemistry calculations combined with electronic spectroscopies, including absorption, fluorescence emission, and excitation, have been used. The formation of successive complexes of stoichiometry (metal/ligand) 1:2, 1:1, and 3:2 has been highlighted. Even under acidic conditions (pH = 4.0), the α-hydroxy-keto function of the molecule presents a high complexing power with regard to copper ions, insofar as a stable complex of 1:2 stoichiometry is obtained with a large conditional stability constant (log β = 8.7). The formation of this predominant species induces a quenching of the dual fluorescence of 3HF, whereas the second complex of stoichiometry 1:1 presents a fluorescence emission.

The acid-base properties of morin and its complexation with the Zn^II cation are investigated by experimental and theoretical approaches.

The stereochemical activity of the lone pair on Pb^II complexes is assessed using several theoretical methods, including structural analyses, computations of Fukui functions, natural bond orbitals, electron localization function, investigation of the electron density and of its laplacian. The attention is focused on four octadentate N-carbamoylmethyl-substituted tetraazamacrocycles of various ring sizes ranging from 8 to 14 atoms associated with the Pb^II cation. The theoretical study illustrates the geometrical constraints imposed by the ring structure which limits the spatial development of the lone pair but without fully preventing it. For a given coordination number, the lone pair activity is strongly correlated to the geometry of the ligand and in particular to the size of the cage that the ligand forms around the Pb^II cation. Some limitations of the theoretical tools used are also evidenced, among them the necessity to sample around a critical point instead of just analyzing its nature. In the case of the laplacian of the electron density, a visualization method is introduced to moderate the results based only on the nature of a critical point. These limitations should also be related to the difficulty to extend the lone pair concept for the heaviest atoms of the classification.