Combined ESR and thermodynamic studies of the superoxide adduct of 5-(diethoxyphosphoryl)-5-methyl-1-pyrroline N-oxide (DEPMPO): hindered rotation around the O-O bond evidenced by two-dimensional simulation of temperature-dependent spectra

Experiments were performed to elucidate the origin of the superhyperfine structure and line width alternation (LWA) seen in the ESR spectrum of the major diastereoisomer (1) of DEPMPO-OOH, the remarkably persistent superoxide adduct of 5-(diethoxyphosphoryl)-5-methyl-1-pyrroline N-oxide (DEPMPO). Using selectively deuterated DEPMPO derivatives, we demonstrated that the superhyperfine pattern can be unambiguously attributed to long-range couplings. The recording in pyridine of highly resolved spectra in a wide temperature range, combined with two-dimensional simulation, allowed us to characterize an inverted LWA in 1 and revealed a uniform line broadening in the spectrum of the minor DEPMPO-OOH diastereoisomer (2), with both effects originating from a chemical exchange between conformers. When the individual spectra of 1 presenting LWA in the fast-exchange regime were simulated, four equally good fits were obtained and this ambiguity could be resolved by using a two-dimensional simulation technique. The thermodynamic and kinetic constants of this exchange were consistent with a rotation around the O-O bond. We propose that line broadening effects in 1 and 2 result from this O-O rotation concerted with the pseudo-rotation of the pyrrolidine ring.     

A new ligand containing a unique combination of backbone- and P-centered chirality: synthesis, resolution and asymmetric catalysis using a chiral enantiopure 2,2′-biphospholene

Enantiopure 2,2'-bi(1-phenyl-3,4-dimethyl-2,5-dihydro-1H-phosphole) has been synthesized and tested in the rhodium-catalyzed asymmetric hydrogenation of -acetamidocinnamic acid. Enantioselectivities up to 75% have been achieved. The absolute configuration of the biphospholene was determined by X-ray diffraction methods on a crystalline tungsten carbonyl derivative.     

Synthesis and characterization of new phosphorus and other heteroatom containing aryl cyanate ester monomers and networks

Several aromatic dicyanate monomers have been synthesized bearing para-linked strong electron withdrawing groups, such as phenylphosphine oxide, sulfone, and carbonyl. These groups increased the reactivity of the cyanate functional groups and eliminated the need for curing catalysts. However, an undesirable decrease in the processing window between the monomer melting point and the onset of cure was also generally observed. An arylene ether phenyl phosphine oxide system was designed that displayed several attractive characteristics such as a low softening point, a wide processing window, cure with no catalyst, high T_g and high char yield in air, suggesting that these new thermosets might show good fire resistance. The dicyanate ester monomers were synthesized in high yield by reacting various bisphenols with cyanogen bromide in the presence of triethylamine. The high reactivity of the cyanate functional groups required that the cyanation reaction be conducted at temperature below 0°C in order to prevent imidocarbonate side reactions. Proton NMR and FT-IR were used to characterize these monomers. The cyclotrimerization curing process was monitored by the disappearance of the carbon-nitrogen triple bond stretch (2270 cm⁻¹). An optimal cure schedule was determined and the cured polycyanurate networks were characterized by DSC, DMTA, and TGA. Tg values were typically > 250°C and 5% weight loss values were observed by TGA in air above 400°C. Several of the dicyanate monomers with sufficiently large processing windows were cured into single lap shear adhesive bonds onto titanium 6/4 and the measurements are reported herein. © 1997 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 35: 977–987, 1997     

Universal interpolating function for the dispersion coefficient of DNA fragments in sieving matrices

The separation of DNA fragments by (slab or capillary) gel electrophoresis has been studied extensively. To characterize the separation achieved by such systems, one needs to understand the impact (and their dependency upon the experimental quantities) of two physical parameters: the electrophoretic mobility mu and the diffusion coefficient D. Three different regimes have been shown to exist for both mu and D: the Ogston regime, the reptation regime and the reptation with orientation regime (note that separation is only possible for the first two regimes). In the small electric field limit, both mu and D are apparently well described by theories for all three regimes. Unfortunately this results in disjointed scaling laws and no theory-based general equations can apply to all regimes. Recently, an empirical interpolating formula has been proposed that adequately fits the low electric field mobility mu of dsDNA fragments across all three regimes and is compatible with accepted theories. In this article we review and clarify the current state of knowledge regarding the size dependence of the mobility and the diffusion coefficient and propose an interpolating formula for molecular size dependence of the low field diffusion coefficient D. With formulas for both the mobility and the diffusion coefficient as a function of the experimental conditions one could, in principle, optimize any gel/polymer matrix-based electrophoresis system for a wide range of DNA molecular sizes.     

On the use of the infinite matrix assumption and associated concepts: A critical review

The infinite matrix assumption is commonly used to derive dose rates in the field of paleodosimetric dating methods. The update of nuclear data allowed calculating new dose rate conversion factors and attenuation factors for taking account of grain size. The relevance of the infinite matrix assumption was found to be limited to specific cases and a discussion of potential errors in estimating dose rates to natural dosimeters in sedimentary media is proposed. A new set of geometric features is shown to be of paramount importance for estimating dose rates in sedimentary media. To quantify these effects, Monte Carlo modelling was applied and the architecture of the programmes is described. It is also shown that proper characterization of sediment samples, coupled to the modelling of radioactivity in these sediments may provide more accurate dose rates to quartz grains, down to the single grain scale.     

A preventive maintenance policy for a continuously monitored system with correlated wear indicators

A continuously monitored system is considered, that gradually and stochastically deteriorates according to a bivariate non-decreasing Lévy process. The system is considered as failed as soon as its bivariate deterioration level enters a failure zone, assumed to be an upper set. A preventive maintenance policy is proposed, which involves a delayed replacement, triggered by the reaching of some preventive zone for the system deterioration level. The preventive maintenance policy is assessed through a cost function on an infinite horizon time. The cost function is provided in full form, and tools are provided for its numerical computation. The influence of different parameters on the cost function is studied, both from a theoretical and/or numerical point of view.     

Syntheses and characterizations of bis(trialkoxysilyl)oligoimides. II. Syntheses and characterizations of fluorinated crosslinkable oligoimides with low refractive indices

Novel crosslinkable fluorinated oligoimides were prepared in two steps. The first involved the synthesis of oligoimides terminated with nadic or allylic double bonds, and the second step was materialized either by a radical addition of mercaptotrialkoxysilane derivatives onto nadic double bonds or a hydrosilylation reaction of hydrogenotrialkoxysilane derivative onto allylic double bonds. Three kinds of crosslinking of the trialkoxysilane end groups were studied. The first kind entailed a thermal self‐crosslinking of trialkoxysilane groups. The second process of crosslinking incorporated a bicomponent system—the crosslinked agent was 1,1,1‐tris(4‐hydroxyphenyl)ethane (TRIOH). The trialkoxysilane groups reacted with the hydroxyl–phenol groups of TRIOH to give thermally stable phenoxysilane bonds as well as a crosslinking network. The last method was also a bicomponent system; the oxalic acid was added into an oligoimide solution where by thermal treatment water was created. The water molecules hydrolyzed the trialkoxysilane groups into silanol groups that polycondensed into a crosslinked network following a sol–gel process. The mechanism of the different crosslinking reactions was investigated by Fourier transform infrared spectroscopy and solid‐state ²⁹Si NMR. The self‐crosslinked material prepared from precursor α,ω‐trimethoxysilyl fluorinated oligomer (M_n = 5500 g · mol^?1) exhibited a 10 wt % loss temperature under air higher than 420 °C and a low birefringence (Δn = 0.008) at 1.300 μm. © 2001 John Wiley & Sons, Inc. J Polym Sci Part A: Polym Chem 39: 2602–2619, 2001     

Enhancing the dienic reactivity of phospholes: an improved access to trivalent 7-phosphanorbornenes.

A structural comparison of 1-cyano- and 1-alkoxy-3,4-dimethylphospholes with 1-benzylphosphole has led to some unexpected conclusions. There is no univocal relationship between phosphole aromaticity and pyramidality at phosphorus. It has been found that both the highly pyramidal 1-cyanophosphole 1 (sigma(CPC angles) = 290 degrees), and the much less pyramidal 1-alkoxyphosphole 6 (sigma(CPC angles) = 310 degrees) have a low Bird aromaticity index (27 for both molecules), when compared to 1-benzylphosphole (sigma(CPC angles) = 303 degrees, BI = 35.5). This low aromaticity is correlated with a high reactivity of the diene in both 1 and 7 (similar to 6) toward acrylonitrile. Good stereochemical control is observed with 7, which gives exclusively the anti,endo [4 + 2] cycloadducts with acrylonitrile and diethyl vinylphosphonate.     

How social interactions within a class depend on the teacher’s assessment of the students’ various mathematical capabilities

In this contribution, we will address from aclinical point of view the issue of the interrelations between the knowledge acquiring processes and the social interactions within a class of mathematics: a) how can the knowledge that is to be acquired determine the kind of social relationship established during a didactic interaction, and b) reciprocally, how can the social relationship already established within the class influence each and every student’s acquisition of knowledge?