Molecular organization of DHP membrane fragments

The phase transition of dihexadecyl phosphate (DHP) bilayered disks has been studied using EPR spectroscopy. In the acid form of DHP, a phase transition temperature exists, that we have monitored through the spin-spin interaction between the nitroxide molecules at high concentration (8%) in DHP bilayers. This spin-spin interaction is due to the gathering of solutes in a fluid defect of the membrane: the border. The fluorescence quenching of two probes by the nitroxide stearic acids in DHP bilayers has been studied by stationary and time-resolved fluorescence measurements. The quenching process is mainly static. Both magnetic and fluorescent probes are localized in the periphery of the bilayered disks. An erratum to this article is available at .     

Photoisomerizable bipyridine ligands and macroligands: absorption, photoisomerization properties and theoretical study.

Two 2,2'-bipyridines, substituted at the 4,4'-positions by p-dialkylaminophenylazostyryl moieties p-R2N-C6H4-N=N-C6H4-CH=CH-[6 a, R2N=nBu2N; 6 b, R2N=(nBu)(C4H8OTHP)N; 6 c, R2N=(nBu)(C4H8OH)N], were successfully synthesized by using Wadworth-Emmons reactions. The X-ray structure of 6 a has been determined. Esterification of 6 c with 2-bromoisobutyroylbromide afforded 6 d. This ligand was used as an initiator for the living radical polymerization of methylmethacrylate (MMA) and gave rise to macroligand 6 e. Thin films of good optical quality were obtained by the spin-coating technique. Photoisomerization experiments were carried out on 6 a in solution and on 6 e in both solution and film, and the kinetics of photochemical (E/Z) and thermal (Z/E) isomerization were investigated. They were found to show Z-E back isomerization typical of aminoazobenzene-type rather than of push-pull-type molecules. Density functional theoretical (TD-DFT) calculations were performed on model compound 6 a' (R2N=Me2N) to understand the structural and electronic transitions of the corresponding E-E, E-Z and Z-Z isomers. It was found that the E-E isomer is almost planar as observed experimentally by X-ray diffraction, whereas the Z-Z isomer, which is 35.4 kcal mol(-1) less stable than the E-E isomer, is nonplanar. The theoretical studies also reveal that several transitions of pi-pi*, n-pi* and charge-transfer (CT) types, are involved in the long-wavelength transition of 6 a (E-E). The same observations can be made for the (Z-Z) isomer, and the TD-DFT simulated spectrum fits quite nicely to the experimental, reproducing and explaining the apparition of a blue-shifted charge-transfer band at 390 nm.     

Reduced Functions, Gradients and Hessians from Fixed-Point Iterations for State Equations

In design optimization and parameter identification, the objective, or response function(s) are typically linked to the actually independent variables through equality constraints, which we will refer to as state equations. Our key assumption is that it is impossible to form and factor the corresponding constraint Jacobian, but one has instead some fixed-point algorithm for computing a feasible state, given any reasonable value of the independent variables. Assuming that this iteration is eventually contractive, we will show how reduced gradients (Jacobians) and Hessians (in other words, the total derivatives) of the response(s) with respect to the independent variables can be obtained via algorithmic, or automatic, differentiation (AD). In our approach the actual application of the so-called reverse, or adjoint differentiation mode is kept local to each iteration step. Consequently, the memory requirement is typically not unduly enlarged. The resulting approximating Lagrange multipliers are used to compute estimates of the reduced function values that can be shown to converge twice as fast as the underlying state space iteration. By a combination with the forward mode of AD, one can also obtain extra-accurate directional derivatives of the reduced functions as well as feasible state space directions and the corresponding reduced or projected Hessians of the Lagrangian. Our approach is verified by test calculations on an aircraft wing with two responses, namely, the lift and drag coefficient, and two variables, namely, the angle of attack and the Mach number. The state is a 2-dimensional flow field defined as solution of the discretized Euler equation under transonic conditions.     

Simultaneous Chemiluminometric Determination of Levodopa and Benserazide in a Multi-pumping Flow System with Multivariate Calibration

An automated multi-pumping flow system is proposed for the simultaneous chemiluminometric determination of benserazide and levodopa using multivariate calibration methods. The developed methodology is based on chemiluminescence (CL) emission generated by the reaction of benserazide with luminol, and on a concurrent inhibiting effect of levodopa on this reaction. A multi-pumping flow system comprising multiple solenoid micro-pumps as the only active components was developed to implement a stopped-flow approach for signal acquisition and processing. Artificial neural networks were used to establish a relationship between the CL emission profile and the concentration of both drugs. The concentration values used to establish the experimental calibration samples were varied between 5 and 30 mg l(-1) for levodopa and between 2.5 and 20 mg l(-1) for benserazide. The proposed method was successfully applied to the simultaneous determination of levodopa and benserazide in pharmaceutical formulations combining both drugs.     

Systèmes aromatiques à 10 électrons π dérivés de l'aza-3a pentalène. IX—etude par RMN de l'équilibre azide/tetrazole dans le cas du tetrazolo [5,1-b] benzothiazole

Azido-tetrazole equilibrium is observed in the case of a solution of tetrazolo [5,1-b] benzothiazole in CDCl₃, using proton magnetic resonance at 250 MHz. Analysis of the spectra obtained yields the chemical shifts and the coupling constants of the two tautomeric forms.     

Investigation of hydroxyl-mediated spectral interference from easily ionized elements in laser-enhanced ionization spectrometry in the 281–285 nm range

The spectral background from 281 to 285 nm in the laser-enhanced ionization (LEI) spectrum of aqueous samples containing easily ionized elements (EIE) at concentrations similar to those found in blood was investigated. A complex, structured spectral background was observed, which appears in the presence of Na or K, but does not match the spectral signature of either element. The same behavior was also observed for Li. It was established that this background originates from an energy transfer between laser-excited hydroxyl (OH) molecules and ground-state EIEs. The intensity of this spectral feature was found to increase with EIE concentration and applied electrode voltage. This unexpected source of spectral interference may complicate the determination of trace metals by LEI in the presence of EIEs, since it can not be prevented by simply avoiding interference from atomic lines.     

Photoisomerization processes in the IR-140 laser dye

The photoisomerization processes in the well known IR-140 laser dye and in the closest relevant DTTC model have been investigated by a mode-locked laser spectroscopy in order to observe the influence of a partial rigidization of the polymethine chain. The kinetic, spectral and thermodynamic parameters have been measured; the correlations between the transient quantum yields and the laser efficiency under flash-lamped pumping are discussed. Evidence is given for a surprising solvent effect upon the photoisomerization process.     

Intercomparisons and development of reference materials for short-term mutagenicity testing

Summary Every new product to be put on the market must be checked by a range of testing procedures so as to assess its toxicity (directive 67/548/EEC). Results from the prescribed reverse mutation assay (Ames test) are part of the consideration of whether the introduction of the product into trade is allowed. Using the above test, European testing laboratories achieved different results for the same substances, false negative and false positive results being obtained. The Community Bureau of Reference (BCR) was requested to undertake a project on short-term mutagenicity testing in order to harmonize results at the European level. The results obtained by a first intercomparison using four direct mutagens showed that further work in this field is necessary. Before starting a second intercomparison using two indirect mutagens, a preliminary study was initiated in order to examine the influence of several important parameters. The aim of this project is to certify highly purified 2-aminoanthracene and benzo(a)pyrene for their mutagenic activity.