Modelisation of the Electric Field Linear Response of an Infinite Aggregate of All-Trans Hexatriene Chains by Electrostatic Interaction Model

A classical electrostatic polarization scheme using the additive distribution procedure has been applied to determine the longitudinal polarizability of an all-trans hexatriene molecule in an infinite stretched fiber. The parameters have been derived from ab initio CPHF/6-31G calculations and the electrostatic scheme has been validated via comparison with ab initio results on small clusters. Upon packing the polarizability of all-trans hexatriene increases by 7%. This small increase results from the balance between the enhancement of the polarizability due to collinear packing and the reduction associated with lateral packing.     

Highly Segregated Lamello‐Columnar Mesophase Organizations and Fast Charge Carrier Mobility in New Discotic Donor–Acceptor Triads

Four new donor–acceptor triads (D–A–D) based on discotic and arylene mesogens have been synthesized by using Sonogashira coupling and cyclization reactions. This family of triads consists of two side‐on pending triphenylene mesogens, acting as the electron‐donating groups (D), laterally connected through short lipophilic spacers to a central perylenediimide (PI), benzo[ghi]perylenediimide (BI), or coronenediimide (CI) molecular unit, respectively, playing the role of the electron acceptor (A). All D–A–D triads self‐organize to form a lamello‐columnar oblique mesophase, with a highly segregated donor–acceptor (D–A) heterojunction organization, consequent to efficient molecular self‐sorting. The structure consists in the regular alternation of two disrupted rows of triphenylene columns and a continuous row of diimine species. High‐resolution STM images demonstrate that PI‐TP2 forms stable 2D self‐assembly nanostructures with some various degrees of regularity, whereas the other triads do not self‐organize into ordered architectures. The electron‐transport mobility of CI‐TP2, measured by time‐of‐flight at 200 °C in the mesophase, is one order of magnitude higher than the hole mobility. By means of this specific molecular designing idea, we realized and demonstrated for the first time the so‐called p–n heterojunction at the molecular level in which the electron‐rich triphenylene columns act as the hole transient pathways, and the coronenediimide stacks form the electron‐transport channels.     

CO2 Capture by Hydroxylated Azine-Based Covalent Organic Frameworks

Covalent organic frameworks (COFs) RIO-13, RIO-12, RIO-11, and RIO-11m were investigated towards their CO₂ capture properties by thermogravimetric analysis at 1 atm and 40 °C. These microporous COFs bear in common the azine backbone composed of hydroxy-benzene moieties but differ in the relative number of hydroxyl groups present in each material. Thus, their sorption capacities were studied as a function of their textural and chemical properties. Their maximum CO₂ uptake values showed a strong correlation with an increasing specific surface area, but that property alone could not fully explain the CO₂ uptake data. Hence, the specific CO₂ uptake, combined with DFT calculations, indicated that the relative number of hydroxyl groups in the COF backbone acts as an adsorption threshold, as the hydroxyl groups were indeed identified as relevant adsorption sites in all the studied COFs. Additionally, the best performing COF was thoroughly investigated, experimentally and theoretically, for its CO₂ capture properties in a variety of CO₂ concentrations and temperatures, and showed excellent isothermal recyclability up to 3 cycles.     

Periodic DFT Study of the Effects of Co-Crystallization on a N-Salicylideneaniline Molecular Switch

This work aims at better understanding the complex effects of co-crystallization on a single salicylideneaniline molecular switch, (E)-2-methoxy-6-(pyridine-3-yliminomethyl)phenol (PYV3), which can tautomerize between an enol and a keto form. A combination of periodic boundary conditions DFT and molecular wavefunction calculations has been adopted for examining a selection of PYV3 co-crystals, presenting hydrogen bonds (H-bonds) or halogen bonds (X-bonds), for which X-ray diffraction data are available. Three aspects are targeted: i) the energy (H-bond strength, enol to keto relative energy, and geometry relaxation energies), ii) the geometrical structure (PYV3 to co-crystal and enol to keto geometrical variations), and iii) the electron distribution (PYV3 to co-crystal and enol to keto Mulliken charge variations). These allow i) explaining the preference for forming H-bonds with the nitrogen of the pyridine of PYV3 with respect to the oxygens and the importance of the crystal field, ii) distinguishing the peculiar behavior of the SulfonylDiPhenol (SDP) coformer, which stabilizes the keto form of PYV3, iii) describing the relative stabilization of the enol form upon co-crystallization (with the exception of SDP) and therefore iv) substantiating the co-crystallization-induced reduction of thermochromism observed for several PYV3 co-crystals.     

Study of active naphtodianthrone St John's Wort compounds by electrospray ionization Fourier transform ion cyclotron resonance and multi‐stage mass spectrometry in sustained off‐resonance irradiation collision‐induced dissociation and infrared multiphoton dissociation modes

Five well‐known active naphtodianthrone constituents of Hypericum perforatum (St John's Wort) extracts have been investigated by electrospray ionization Fourier transform ion cyclotron resonance mass spectrometry (ESI‐FTICRMS) and ESI‐FTICRMSⁿ. The studied compounds were hypericin, pseudohypericin, protohypericin, protopseudohypericin (biosynthetic precursors of the two former compounds, respectively) and isopseudohypericin (alkaline degradation product of pseudohypericin). Dissociation mass spectrometry measurements performed on the [M–H]^? ion presented a variable efficiency as a function of the used activation mode. Sustained off‐resonance irradiation collision‐induced dissociation (SORI–CID) only led to a restricted number of fragment ions. In contrast, IRMPD ensured the detection of numerous product ions. Ions detected in ESI‐FTICRMS and ESI‐FTICRMSⁿ experiments were measured with a very high mass accuracy (typically mass error is lower than 0.5 mDa at m/z close to 500) that allowed unambiguous formulae to be assigned to each signal observed in a mass spectrum. In spite of similar structures, specific fragmentation patterns were observed for the different compounds investigated. This study may be useful in the future to characterize in natural extracts these compounds (or derivatives of these compounds) by liquid chromatography/tandem mass spectrometry (LC/MS/MS) experiments by considering the MS/MS transitions highlighted in this paper. Copyright © 2009 John Wiley & Sons, Ltd.     

An experimental and kinetic modeling study on the oxidation of 1,3-dioxolane

The modern catalytic or enzymatic advances allow the production of novel biofuel. Among them, 1,3-dioxolane can be produced from formaldehyde and ethylene glycol, both can be obtained from biomass. In this study, the oxidation of 1,3-dioxolane is studied at stoichiometric conditions. The ignition delay times of 1,3-dioxolane/O₂/inert mixtures were measured in a shock tube and in a rapid compression machine at pressures of 20 to 40 bar and temperatures ranging from 630 to 1300 K. The pressure profiles recorded in the rapid compression machine show a first stage of ignition enlightening the influence of the low temperature chemistry of combustion. Furthermore, mole fraction profiles of the stable intermediates produced during the oxidation of 1,3-dioxolane were measured in a jet-stirred reactor at 10 bar. Following these observations, a detailed kinetic model was developed with reaction rate coefficients and thermochemical data calculated by theoretical calculations or estimated by analogies to suitable molecules. In order to get an insight into the most important reaction pathways brute force sensitivity analysis and reaction pathway analysis were performed with the proposed model and discussed. It became clear that in the fuel-in-air case for the alkylhydroperoxide of 1,3-dioxolane the ring opening beta-scission pathway is favored against the further alkane-like second addition to molecular oxygen, which leads to a limited negative temperature coefficient.     

Quelques modèles diffusifs capillaires de type KortewegSome diffusive capillary models of Korteweg type.

The purpose of this Note is to propose new diffusive capillary models of Korteweg type and discuss their mathematical properties. More precisely, we introduce viscous models which provide some additional information on the behavior of the density close to vacuum. We actually prove that if some compatibility conditions between diffusion and capillarity are satisfied, some extra regularity information on a quantity involving the density is available. We obtain a non-trivial equality deduced from the special structure of the momentum equation. This Note generalizes to some extent the authors' previous works on the Korteweg model (with constant capillary coefficient) and on the shallow water equation. To cite this article: D. Bresch, B. Desjardins, C. R. Mecanique 332 (2004).     

Theoretical and experimental investigation of the structural and spectroscopic properties of coumarin 343 fluoroionophores

A joint theoretical-experimental investigation has been carried out to unravel the details of the complexation of cations by fluoroionophores based on coumarin 343 and to interpret the modifications in the ligand and also in the coumarin structural, electronic, magnetic, and vibrational properties. It is confirmed that C343-dea (1) complexes the cations by both the lactone and the amide oxygen atoms whereas for C343-crown (2) and C343-dibenzocrown (3), the cations are complexed by the oxygen atoms of the lactone as well as those of the crown ligand. These complexations induce geometric modifications, which are delocalized over the coumarin backbone and are related to electronic reorganizations that modify the spectroscopic signatures. This paper analyzes these signatures and shows how they are related as well as how they can be used to monitor the complexation process. Upon complexation, the UV-visible absorption spectra display a bathochromic shift of the most intense electronic transition; this shift is generally larger for the most flexible compound 1 as well as when complexing divalent cations. NMR spectra bear many signatures of the complexation, of which the most remarkable ones are the large shielding of C(1) and the large deshieldings of C(9) and C(16). Additional makers of complexation are highlighted in the IR vibrational spectra, in particular the bands associated with the lactone and amide CO vibrations, which are downshifted when the corresponding CO is involved in the complexation mode and, otherwise, upshifted. A high degree of consistency characterizes the different geometrical, electronic, magnetic, and vibrational signatures, which substantiates the assignment of the modes of complexation in 1-3. In addition, the agreement between the experimental data and the theoretical values is rather satisfactory, in that it at least enables us to interpret the spectral signatures.