Quelques considérations sur la structure électronique du naphtalène

Theπ electronic structure of naphtalene is studied, using a semi-empirical approximation for coulombic and resonance integrals; forH andS (H, hamiltonian;S, overlap) the complete matrices are adopted, together withKohlrausch's nuclear effective charges. A non uniform charge distribution is obtained, with charge accumulation at the tertiary carbons. Bond orders between non neighboring atoms indicate contributions to the fundamental state from other structures besides the classical ones. A comparative study of the obtained interatomic distances is carried. It is shown that [H, S]=0 is not a sufficient condition for the identity of the bond orders for the fundamental state calculated with and without overlap.     

High-resolution heteronuclear correlation spectroscopy in solid state NMR of aligned samples

A new two-dimensional scheme is proposed for accurate measurements of high-resolution chemical shifts and heteronuclear dipolar couplings in NMR of aligned samples. Both the (1)H chemical shifts and the (1)H-(15)N dipolar couplings are evolved in the indirect dimension while the (15)N chemical shifts are detected. This heteronuclear correlation (HETCOR) spectroscopy yields high-resolution (1)H chemical shifts split by the (1)H-(15)N dipolar couplings in the indirect dimension and the (15)N chemical shifts in the observed dimension. The advantages of the HETCOR technique are illustrated for a static (15)N-acetyl-valine crystal sample and a (15)N-labeled helical peptide sample aligned in hydrated lipid bilayers.     

Early stage expansion and time-resolved spectral emission of laser-induced plasma from polymer

In the nanosecond laser ablation regime, absorption of laser energy by the plasma during its early stage expansion critically influences the properties of the plasma and thus its interaction with ambient air. These influences can significantly alter spectral emission of the plasma. For organic samples especially, recombination of the plasma with the ambient air leads to interfering emissions with respect to emissions due to native species evaporated from the sample. Distinguishing interfering emissions due to ambient air represents a critical issue for the application of laser-induced breakdown spectroscopy (LIBS) to the analysis of organic materials. In this paper, we report observations of early stage expansion and interaction with ambient air of the plasma induced on a typical organic sample (nylon) using time-resolved shadowgraph. We compare, in the nanosecond ablation regime, plasmas induced by infrared (IR) laser pulses (1064 nm) and ultraviolet (UV) laser pulses (266 nm). Nanosecond ablation is compared with femtosecond ablation where the post-ablation interaction is absent. Subsequent to the early stage expansion, we observe for each studied ablation regime, spectral emission from CN, a typical radical for organic and biological samples. Time-resolved LIBS allows identifying emissions from native molecular species and those due to recombination with ambient air through their different time evolution behaviors.     

Femtosecond Laser-Induced Breakdown Spectroscopy for Detection of Trace Elements in Sophora Leaves

Sophora leaves from several areas in Beijing are analysed by femtosecond laser-induced breakdown spectroscopy （femto-LIBS）. Although the used spectral detection system is not time-resolved, the spectral lines of trace mineral elements are detected and analysed. It is proven that the femto-LIBS can be an efficient method to detect mineral trace elements contained in tree leaves which is a biomonitor for atmospheric pollution assessment or botanic studies. An interesting case of correlation between trace elements detected in tree leaves and the pollution of the concerned area is presented, for the first time to our knowledge.     

Optical characterization of photochromic effect

Photochromic powders are powders whose color is sensitive to UV irradiation. When such a powder is exposed to the sunlight or any other UV rays, it becomes darker and then looks back progressively to its initial color. An optical method has been set up in order to quantify these colors variations. We can then quantify the variations in the colorimetric space, and the time response of the coming back phenomenon.     

DFT and NMR parameterized conformation of valeranone

A Monte Carlo random search using molecular mechanics, followed by geometry optimization of each minimum energy structure employing density functional theory (DFT) calculations at the B3LYP/6-31G* level and a Boltzmann analysis of the total energies, generated accurate molecular models which describe the conformational behavior of the antispasmodic bicyclic sesquiterpene valeranone (1). The theoretical H-C-C-H dihedral angles gave the corresponding 1H, 1H vicinal coupling constants using a generalized Karplus-type equation. In turn, the 3J(H,H) values were used as initial input data for the spectral simulation of 1, which after iteration provided an excellent correlation with the experimental 1H NMR spectrum. The calculated 3J(H,H) values closely predicted the experimental values, excepting the coupling constant between the axial hydrogen alpha to the carbonyl group and the equatorial hydrogen beta to the carbonyl group (J(2beta, 3beta)). The difference is explained in terms of the electron density distribution found in the highest occupied molecular orbital (HOMO) of 1. The simulated spectrum, together with 2D NMR experiments, allowed the total assignment of the 1H and 13C NMR spectra of 1.     

Direct zonal liquid chromatographic method for the kinetic study of actinomycin-DNA binding

The binding of an anticancer drug (actinomycin D or ACTD) to double-stranded DNA (dsDNA) was studied by means of high-performance liquid chromatography (HPLC). ACTD is an antitumor antibiotic containing one chromophore group and two pentapeptidic lactone cycles that binds dsDNA. Incubations of ACTD with DNA were performed at physiological pH. The complexed and free ligand concentrations of the mixture were quantified at 440 nm from their separation on a size-exclusion chromatographic (SEC) column using the same buffer for the elution and the sample incubation. The DNA and the ACTD-DNA complexes were eluted at the column exclusion volume while the ligand was retained on the support. An apparent binding curve was obtained by plotting the amount emerging at the exclusion column volume against that eluted at free ACTD retention volume. A dissociating effect was evidenced and the binding parameters were significantly different from those obtained at equilibrium by visible absorbance titration. The equilibrium binding parameters determined by absorption spectroscopy were used as starting data in the numerical simulations of the chromatographic process. The results showed a strong dependency of the apparent binding parameters on the reaction kinetics. Finally the comparison of the apparent binding curve obtained from the HPLC experiments and from the numerical simulations permitted an evaluation of the dissociation rate constant (kd = 0.004 s(-1)).     

Role of interfacial chemistry on the rheology and thermo-mechanical properties of clay-polymer nanocomposites for building applications

This study is directed towards investigating the role of the surface treatment of clay particles on the rheological and thermomechanical behaviour of clay-epoxy blends. Nanocomposites were prepared by mixing small amounts (5–10 mass %) of commercial organoclays or raw clays with an epoxy system commonly used in civil engineering. Rheological characterisations in the liquid state revealed a pronounced thixotropic character of the organoclay-based systems, which all exhibited a shear-thinning behaviour above a critical stress threshold (yield stress), depending on both the intensity of interfacial interactions and the degree of filler dispersion. On the other hand, systems based on raw clay particles behaved like Newtonian fluids, in the same way as the unreinforced polymer matrix. Complementary dynamic mechanical analyses (DMA) performed on the cured cross-linked nanocomposites also showed significant changes in the viscoelastic behaviour of the epoxy matrix due to the introduction of organoclays, whereas only minor variations were observed following the introduction of raw fillers. These results were consistent with nanoscale morphological characterisations performed by conventional X-ray diffraction (XRD) on the various hybrid systems. In this context, rheology and DMA appear as attractive alternative methods for assessing the filler dispersion at a macroscopic (and possibly more relevant) scale. This research is of practical interest for civil engineers, since clay reinforced-epoxies could in the future be used as coating materials with enhanced barrier performances, in order to protect infrastructures against environmental ageing or corrosion.     

The Antiepileptic Lamotrigine and Its Analogues: Comparative Theoretical Electronic Properties

Electronic properties of lamotrigine (LTG) and two analogues (A1 and A2) are compared through MOPAC-AM1 calculations. Two stable conformers of LTG are calculated to exist in agreement with X-ray crystallography. In the three compounds and the two conformers for each of them, the more favorable protonation sites are N₂ and N₄; these should then be the sites appropriate for interaction with a receptor, and group valence reinforces the supposition. The molecular electrostatic potentials show that a region between the two chlorine atoms in LTG could be the site for an electrostatic interaction with a corresponding site in the receptor. The fluorine atom in A1 would play an equivalent role. A simple model for LTG-receptor interaction is proposed.