Evidence of a critical content in Fe(0) on FoCa7 bentonite reactivity at 80 °C

In order to assess the evolution of the confinement properties of clay engineered barriers (EBS) when in contact with metallic canisters containing radioactive wastes, Fe(0)-bentonite interactions need to be assessed. “45 days–80 °C” tests were performed using powdered FoCa7 bentonite and metallic iron. Since one fundamental parameter may be the available quantity of Fe(0), a wide range of Iron/Clay mass ratios (I/C) from 0 to 1/3 is used. The confinement power of clay material results from the swelling properties and the retention capacity. Thus, the major criterion which is chosen to assess the evolution of the confinement properties in this study is the variation of Cation Exchange Capacity (CEC). In parallel, the physico-chemical evolution of bentonite is studied using XRD and EDS-TEM microanalyses. The evolution of the distribution of iron environments is obtained by ⁵⁷Fe Mössbauer spectroscopy.This study evidences that both kaolinite and smectite from the bentonite are altered into SiAlFe gels when in contact with Fe(0). These gels maturates into Fe-rich di-trioctahedral phyllosilicates, whose composition is bounded by the one of odinite and greenalite in a Fe–M⁺–4Si diagram when I/C = 1/3. Most of all, it is evidenced that the reaction depends on the available quantity of Fe(0). When the I/C ratio is between 1/30 and 1/7.5, the exchange capacity of FoCa7 bentonite starts decreasing, the consumption of Fe(0) becomes significant, the alteration of smectites occurs and secondary oxides are formed. The crystallization of Fe-rich phyllosilicates is observable when I/C ratio is higher, from a threshold between 1/7.5 and 1/5. Above I/C = 1/3.75, initial iron oxides are strongly consumed and participate in the incorporation of Fe²⁺ and Fe³⁺ in gels or new phyllosilicates octahedra.These experimental results were used as input data for the prediction of the long-term evolution of the EBS using Crunch reaction-transport model.     

One Question,Multiple Answers: Biochemical and Biophysical Screening Methods Retrieve Deviating Fragment Hit Lists

Fragment‐based lead discovery is gaining momentum in drug development. Typically, a hierarchical cascade of several screening techniques is consulted to identify fragment hits which are then analyzed by crystallography. Because crystal structures with bound fragments are essential for the subsequent hit‐to‐lead‐to‐drug optimization, the screening process should distinguish reliably between binders and non‐binders. We therefore investigated whether different screening methods would reveal similar collections of putative binders. First we used a biochemical assay to identify fragments that bind to endothiapepsin, a surrogate for disease‐relevant aspartic proteases. In a comprehensive screening approach, we then evaluated our 361‐entry library by using a reporter‐displacement assay, saturation‐transfer difference NMR, native mass spectrometry, thermophoresis, and a thermal shift assay. While the combined results of these screening methods retrieve 10 of the 11 crystal structures originally predicted by the biochemical assay, the mutual overlap of individual hit lists is surprisingly low, highlighting that each technique operates on different biophysical principles and conditions.     

Benzophenone vs. Copper/Benzophenone in Light‐Promoted Atom Transfer Radical Additions (ATRAs): Highly Effective Iodoperfluoroalkylation of Alkenes/Alkynes and Mechanistic Studies

Iodoperfluooralkylation of terminal alkenes and alkynes is effectively photo‐promoted by benzophenone 2 (BP) or the photoreducible copper(II) complex 1 . In particular, BP at 1 mol% in methanol upon 365 nm irradiation with a low‐pressure mercury lamp (type TLC=thin layer chromatography, 6 W) results in a fast reaction with excellent reaction yields. Complex 1 and BP 2 exhibited very similar reactivity, suggesting that the reactions involving 1 are likely to be governed by the benzophenone photoactivation processes, rather than copper(I)/(II) redox processes. Mechanistic investigations using transient absorption spectroscopy revealed that a deactivation pathway of the benzophenone triplet (³BP*) is via its reaction with the methanol solvent. We propose that the generated radicals, in particular ^.CH₂OH, play a key role in the initiation step forming R_f^. by reacting with R_fI, R_f^. then entering a radical chain cycle. ¹H NMR studies provided evidence that a substantial amount (∼7% NMR yield) of the hemiacetal CH₃OCH₂OH is formed, i.e., the possible by‐product of the reaction between ^.CH₂OH and R_fI. Finally, DFT calculations indicate that a triplet‐triplet energy transfer (TTET) process from ³BP* to perfluorooctyl iodide (C₈F₁₇I) is unlikely or should be rather slow under the reaction conditions, consistent with the transient absorption studies.

     

An application of the thermo-radiative model SOLENE for the evaluation of street canyon energy balance

This paper presents a validation of the thermo-radiative model SOLENE and its application for analysing the street canyon energy balance. The validation data were selected from the temperature and radiation measurements obtained during the JAPEX campaign, previously described by Idczak et al. [16]: a set of four lines of steel containers buildings composing three parallel street canyons at an approximate 1:5 scale. Reference weather data and micrometeorological conditions within the canyon were measured. Numerical simulations were carried out using the meteorological measurements as model inputs. The simulated surface temperatures and radiation fluxes are compared with the measurements for a full week period, with a focus on a day with clear sky conditions. The street canyon energy balance analysis demonstrates that the most energetic surface was the street ground due to its thick surface layer of tar-coated gravels while the walls had a low heat capacity. The thermal radiation balance was negative for all canyon surfaces. The sensible heat was transferred mainly from the canyon surfaces to the ambient air, but also from the air to the ground in the morning. The effective albedo of the canyon had a diurnal value of 0.20–0.25, but dropped to 0.10 in the afternoon when the ground strongly transformed the direct and reflected solar radiation into sensible heat. This narrow street configuration enhanced solar radiation absorption and longwave radiation trapping.     

Immobilization of polyisobutene in semi-interpenetrating polymer network architecture

The entrapment of linear polyisobutene (PIB) in semi-IPN architecture is shown to be as efficient as it is in cross-linkable telechelic PIB based full IPN architectures as far as the suppression of cold flow is concerned. Indeed, homogeneous linear PIB/cross-linked polycyclohexylmethacrylate (PCHMA) semi-IPNs containing from 20 to 70 wt% PIB and synthesized without solvent show no cold flow and higher mechanical properties than those of linear PIB or 50 wt% PIB containing blend. In addition, the particular barrier properties toward gas and water are preserved. Those properties arise from the phase co-continuity morphology of the semi-IPN materials which moreover compares with that of corresponding IPNs. A systematic study of the synthesis conditions (nature of the initiator, temperature, cross-linking density) showed that the reacting mixture viscosity is an important parameter that controls the phase separation degree in the final material.     

Use of an artificial neural network algorithm to predict hydrate dissociation conditions for hydrogen+water and hydrogen+tetra-n-butyl ammonium bromide+water systems

In this communication, a feed-forward artificial neural network algorithm is developed to estimate the hydrate dissociation conditions for the hydrogen+water and hydrogen+tetra-n-butyl ammonium bromide+water systems. To develop this algorithm, the experimental data reported in the literature for hydrate dissociation conditions of the latter two systems with different concentrations of tetra-n-butyl ammonium bromide in aqueous phase below its stoichiometric concentration (i.e., ≈0.037 mole fraction or 0.43 mass fraction) have been used. Independent experimental data (not used in training and developing this algorithm) have been employed to examine the reliability of this method. It is shown that the predicted and the experimental data are in acceptable agreement demonstrating the reliability of this algorithm as a predictive tool.     

Axial impeller selection for anchorage dependent animal cell culture in stirred bioreactors: Methodology based on the impeller comparison at just-suspended speed of rotation

Animal cells, which are nowadays essential for the industrial production of proteinic compounds, are commonly cultivated inside stirred tank bioreactors. In case of anchorage dependent cells, they are usually fixed on microcarriers. The choice of agitation conditions (impeller type, rotational speed…) in this type of process is not an easy task as it has to fulfil three potentially conflicting goals: (1) maintaining microcarriers in complete suspension, (2) homogenizing the culture medium, and (3) limiting mechanical constraints generated by the hydrodynamics on the cells. The aim of this study is to present an original methodology to select the most appropriate axial impeller for this specific application. Seven propellers are preselected on basis of their characteristics available in the literature. Instead of comparing impellers at a given rotational speed or a given power input, they are compared at their respective minimum impeller rotational speed that leads to a complete microcarrier suspension, i.e. at their respective just-suspended speed N_js. They are then compared at higher rotational speeds N, expressed as multiples of N_js. The impeller classification is based on the intensity of mechanical constraints they produced, evaluated from: (1) the macro-shear rate quantified by the spatial derivative of time average velocity fields measured by P.I.V., (2) the micro-shear rate characterized by the ratio between the microcarrier diameter to the average Kolmogorov scale computed from power input measurements, and (3) the impact of microcarrier collisions on cells described via the turbulent collision severity index also computed from power input measurements. Results show that the 125 mm diameter TTP impeller (Mixel) and the 150 mm diameter Elephant Ear impeller (Applikon) produce the smallest mechanical constraints at their just-suspended speed (50 and 20 rpm, respectively). Moreover, the mechanical constraints they produce increase more slowly with the N/N_js ratio than the mechanical constraints produced by other impellers. These propellers are thus even more advantageous if rotational speeds higher than the just-suspended speed have to be used.     

Effect of calcium chloride on mechanical properties and microbiological characteristics of cv. Conservolea naturally black olives fermented at different sodium chloride levels

The effect of calcium chloride (CaCl₂)(5 gL^?1) and sodium chloride (NaCl) concentration (40, 60 and 8 gL^?1) on the microbiological and mechanical properties of naturally black olives of cv. Conservolea in brines was studied. In 40 and 60 g L^?1 brines the growth of lactic acid bacteria was favoured over that of yeasts, resulting in rather complete lactic acid fermentation as indicated by high free acidity (9.8–11.5 g lactic acid L^?1) and low pH (3.7–3.8). At 80 g L^?1 brine, yeasts were the dominant members of the microflora, rendering a product with lower acidity (8 g lactic acid L^?1) and higher pH (4.3–4.5). In the presence of CaCl₂ there was a consistent increase in the depth of the peripheral region in which cell wall breakage occurred. When cells separated, perforated walls were observed at sites associated with plasmodesmata. The flesh was strongest and stiffest when CaCl₂ was added to olives treated with 40 g L^?1 brine, consistent with cell wall breakage being the predominant mode of failure. The only observed effect on the mechanical properties of the skin was a stiffening at 60 g L^?1 brine on addition of CaCl₂. Copyright © 2007 Society of Chemical Industry     

Druids' Knowledge in Chemical Engineering: Analysis of the Illustrated Literature by Goscinny and Uderzo

The illustrated literature series Asterix (and Obelix) is commonly known as entertainment and distraction, but behind that mask, case studies for chemical production in small medium enterprises and the crucial role of research and development can be discovered. The series rightly puts chemistry and chemical engineering at the heart of success and prosperity. Overall, the motives exemplified are of high relevance today for chemical industry.     

HDN of 1–4 tetrahydroquinoline over MoNxOy and NbNxOy: effect of transition metal, solvent and ammonia

Oxynitrides of early transition metals are bifunctional catalysts active in hydrodenitrogenation (HDN). The strength of the hydrogenating function and the acidic properties of molybdenum and niobium oxynitrides were investigated, as well as the inhibiting effect of ammonia and the effect of solvent (cyclohexane or tetradecane) on HDN of 1,2,3,4‐tetrahydroquinoline (1–4 THQ). Even under high hydrogen pressure (4.5 MPa) the reaction was found to be able to proceed without hydrogenation of the aromatic cycle of 1–4 THQ before C–N bond scission, which is not the case over sulfided NiMo supported catalysts in HDN. Experiments in presence of ammonia permitted to support a bifunctional dual site concept. This revised version was published online in July 2006 with corrections to the Cover Date.