Naphthalimide‐phthalimide derivative based photoinitiating systems for polymerization reactions under blue lights

Naphthalimide‐phthalimide derivatives (NDPDs) have been synthesized and combined with an iodonium salt, N‐vinylcarbazole, amine or 2,4,6‐tris(trichloromethyl)‐1,3,5‐triazine to produce reactive species (i.e., radicals and cations). These generated reactive species are capable of initiating the cationic polymerization of epoxides and/or the radical polymerization of acrylates upon exposure to very soft polychromatic visible lights or blue lights. Compared with the well‐known camphorquinone based systems used as references, the novel NDPD based combinations employed here demonstrate clearly higher efficiencies for the cationic polymerization of epoxides under air as well as the radical polymerization of acrylates. Remarkably, one of the NDPDs (i.e., NDPD2) based systems is characterized by an outstanding reactivity. The structure/reactivity/efficiency relationships of the investigated NDPDs were studied by fluorescence, cyclic voltammetry, laser flash photolysis, electron spin resonance spin trapping, and steady state photolysis techniques. The key parameters for their reactivity are provided. © 2014 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2015 , 53, 665–674     

Convergence of the parabolic Ginzburg–Landau equation to motion by mean curvature

We present some new results for the asymptotic behavior of the complex parabolic Ginzburg–Landau equation. In particular, we establish that, as the parameter ε tends to 0, vorticity evolves according to motion by mean curvature in Brakke's weak formulation. The only assumption we make is a natural energy bound on the initial data. In some cases, we also prove convergence to enhanced motion in the sense of Ilmanen. To cite this article: F. Bethuel et al., C. R. Acad. Sci. Paris, Ser. I 336 (2003).     

Evidence of a worldwide stock market log-periodic anti-bubble since mid-2000

Following our investigation of the USA Standard and Poor index anti-bubble that started in August 2000 (Quant. Finance 2 (2002) 468), we analyze 38 world stock market indices and identify 21 “bearish anti-bubbles” and six “bullish anti-bubbles”. An “anti-bubble” is defined as a self-reinforcing price trajectory with self-similar expanding log-periodic oscillations. Mathematically, a bearish anti-bubble is characterize by a power law decrease of the price (or of the logarithm of the price) as a function of time and by expanding log-periodic oscillations. We propose that bearish anti-bubbles are created by positive price-to-price feedbacks feeding overall pessimism and negative market sentiment further strengthened by inter-personal interactions. Bullish anti-bubbles are here identified for the first time. The most striking discovery is that the majority of European and Western stock market indices as well as other stock indices exhibit practically the same log-periodic power law anti-bubble structure as found for the USA S&P500 index. These anti-bubbles are found to start approximately at the same time, August 2000, in all these markets. This shows a remarkable degree of worldwide synchronization. The descent of the worldwide stock markets since 2000 is thus an international event, suggesting the strengthening of globalization.     

A new approach towards peptidosulfonamides: synthesis of potential inhibitors of bacterial peptidoglycan biosynthesis enzymes MurD and MurE

Peptidosulfonamides are an emerging group of peptidomimetics with a variety of applications in medicinal chemistry. We present a novel approach to the synthesis of peptidosulfonamides, and apply it to a series of new potential inhibitors of the bacterial peptidoglycan biosynthesis enzymes MurD and MurE. The synthesis was conducted via N-phthalimido β-aminoethanesulfonyl chlorides, which are new building blocks for the synthesis of peptidosulfonamides. In the most crucial step, sulfonic acids or their sodium salts were converted into the corresponding sulfonyl chlorides using an excess of either SOCl₂ or SOCl₂/DMF, and then coupled to the C-protected amino acid. None of the compounds significantly inhibited MurD, however, some inhibited MurE; one had an IC₅₀ below 200 μM, which constitutes a promising starting point for further development. Molecular modelling simulations were performed on two analogues to investigate the absence of inhibitory activity of the sulfonamide compounds on MurD.     

Dynamics of multiple degree Ginzburg–Landau vortices

For the two-dimensional complex parabolic Ginzburg–Landau equation we prove that, asymptotically, vortices evolve according to a simple ordinary differential equation, which is a gradient flow of the Kirchhoff–Onsager functional. This convergence holds except for a finite number of times, corresponding to vortex collisions and splittings, which we describe carefully. The only assumption is a natural energy bound on the initial data. To cite this article: F. Bethuel et al., C. R. Acad. Sci. Paris, Ser. I 342 (2006).     

Toward phenanthridin-2-ylidene: electrophilicity versus acidity in planar-constrained C-aryl iminium salts

A phenanthridinium salt was prepared in four steps, including an intramolecular CH-arylation and a hydride abstraction reaction. Treatment with sterically demanding bases does not lead to the corresponding carbene, but rather to addition products: the planar-constrained geometry significantly enhances the electrophilicity over the acidity of C-aryl iminium salts.     

The composition analysis of YBa2Cu3O7-δ or PrBa2Cu3O7-δ thin films and (YBa2Cu3O7-δ/PrBa2Cu3O7-δ)n heterostructures prepared by CVD

Some YBa₂Cu₃O_7-δ films and heterostructures prepared by Chemical Vapor Deposition (CVD) were analyzed in our laboratories by EPMA-EDX or WDX, RBS, SNMS and AES. It was found that in some cases the results of composition analysis can significantly deviate from each other. At least two main reasons for these deviations exist: the different lateral resolution and the application of different reference samples for the calibration. Received: 3 June 1996 / Revised: 14 October 1996 / Accepted: 16 October 1996     

Fe(CO)5 thin films adsorbed on Au(111) and on self-assembled organic monolayers: I. Structure

The adsorption of Fe(CO)(5) onto Au(111)/mica and C(4), C(8), C(12), and C(16) SAMs/Au(111)/mica surfaces has been studied using infrared spectroscopy to elucidate the coverage-dependent structures of these films and the intermolecular couplings that determine the form of the spectra. For all substrates, the first layer is composed of molecules physisorbed with one axial and two equatorial carbonyl groups directed toward the substrate; subsequent layers are preferentially oriented with the C(3) molecular axis aligned perpendicular to the substrate (i.e., one axial carbonyl group directed toward the substrate). The axial vibrational band systematically shifts to higher frequencies with increasing surface coverage because of the effects of intermolecular coupling of the quasiparallel transition dipole moments. The strong effects of dipolar coupling are also witnessed by the trends of the band positions when the distance to the image plane is systematically varied using highly organized self-assembled organic substrates; no band shifts are observed when dilute Fe(CO)(5) is embedded in Xe matrixes under identical experimental conditions. The as-deposited films are structurally stable below 125 K on Au(111)/mica surfaces and below 100 K on the organic self-assembled monolayers. The instability of the films above these temperatures demonstrates that the as-adsorbed films do not form thermodynamically well-defined phases but are structurally metastable. The results presented herein and in the companion paper provide a consistent framework to interpret the spectroscopy of these systems that resolves outstanding issues concerning these films and provides a structural model that explains the dynamic properties of these films during exposure to low-energy electron beams.     

Assignment of the EPR spectrum of 5,5-dimethyl-1-pyrroline N-oxide (DMPO) superoxide spin adduct

[structure: see text] Spin trapping consists of using a nitrone or a nitroso compound to "trap" an unstable free radical as a long-lived nitroxide that can be characterized by electron paramagnetic resonance (EPR) spectroscopy. The formation of DMPO-OOH, the spin adduct resulting from trapping superoxide (O(2)(*)(-)) with 5,5-dimethyl-1-pyrroline N-oxide (DMPO), has been exploited to detect the generation of superoxide in a wide variety of biological and chemical systems. The 12-line EPR spectrum of DMPO-OOH has been either reported or mentioned in more than a thousand papers. It has been interpreted as resulting from the following couplings: A(N) approximately 1.42 mT, A(H)beta approximately 1.134 mT, and A(H)gamma(1H) approximately 0.125 mT. However, the DMPO-OOH EPR spectrum has an asymmetry that cannot be reproduced when the spectrum is calculated considering a single species. Recently, it was proposed that the 0.125 mT splitting was misassigned and actually results from the superimposition of two individual EPR spectra associated with different conformers of DMPO-OOH. We have prepared 5,5-dimethyl-[3,3-(2)H(2)]-1-pyrroline N-oxide (DMPO-d(2)), and we showed that the EPR spectrum of the corresponding superoxide spin adduct is composed of only six lines, in agreement with the assignment of the 0.125 mT splitting to a gamma-splitting from a hydrogen atom bonded to carbon 3 of DMPO. This result was supported by DFT calculations including water solvation, and the asymmetry of the DMPO-OOH EPR spectrum was nicely reproduced assuming a chemical exchange between two conformers.