Influence of fillers on mechanical properties of ATH filled EPDM during ageing by gamma irradiation

The presence of a significant content of fillers accelerates the degradation of ATH filled EPDM subjected to gamma irradiation at room temperature. Above the melting temperature of the EPDM, this induces a decrease in the apparent mechanical reinforcement of the fillers. This also promotes de-cohesion mechanisms which leads to an increase in the strain at break with irradiation dose. It is not clear whether the use of a filler treatment attenuates this accelerating effect or not; however, part of this treatment remains efficient at a high dose and seems also to delay but not suppress the occurrence of de-cohesion mechanisms at large strain. Moreover, at room temperature, i.e. below the melting temperature, all the consequences of ageing by gamma irradiation are strongly attenuated by the presence of a semi-crystalline microstructure, the morphology of which is not too strongly modified by irradiation.     

Efficient hydrogen peroxide generation from organic matter in a bioelectrochemical system

Hydrogen peroxide (H₂O₂) is an important industrial chemical, but its current production methods are highly energy-intensive. This study presents a novel process for the production of H₂O₂ based on the bioelectrochemical oxidation of wastewater organics at an anode coupled to the cathodic reduction of oxygen to H₂O₂. At an applied voltage of 0.5 V, this system was capable of producing 1.9 ± 0.2 kg H₂O₂/m³/day from acetate at an overall efficiency of 83.1 ± 4.8%. As most of the required energy was derived from the acetate, the system had a low energy requirement of 0.93 kWh/kg H₂O₂.     

Approximating a real number by a rational number with a limited denominator: A geometric approach

We consider the problem of determining the rational number which best approximates the real number a and such that its denominator belongs to an interval [b,b^′]. There is a related geometric problem consisting in finding the integer point lying in the vertical domain D of the form {(x,y)∈R²∣b≤x≤b^′} such that the straight line passing through the origin and through this point best approximates the straight line L of slope a passing through the origin. The computation of this point is interlinked with the computation of both the convex hulls of the integer points located above and below the straight line L respectively and lying in the vertical domain D. In the literature, many general convex hull algorithms exist, as the gift wrapping algorithm for example. However, we focus on two interesting approaches to compute these convex hulls which are especially appropriated in our special configuration. The first one mainly uses number theory and runs in O(log(b^′)) time. The other is in line with computational geometry as the method proposed in 1999 by Balza-Gomez et al. [H. Balza-Gomez, J.-M. Moreau, D. Michelucci, Convex hull of grid points below a line or a convex curve, in: DGCI ’99: Proceedings of the 8th International Conference on Discrete Geometry for Computer Imagery, Springer, Marne-la-Vallée, France, 1999, pp. 361-374] which runs in O(log(b^′−b)) time. We propose a new method for the computation of these convex hulls which combines number theory and computational geometry. Our method preserves the optimal time complexity and is the first being output sensitive. Indeed, we compute the convex hulls in time linear in their vertex number. Moreover, the resulting algorithm is very simple and so is suitable for implementation.     

Time resolved three-dimensional acousto-optic imaging of thick scattering media

Acousto-optic imaging is based on light interaction with focused ultrasound in a scattering medium. Thanks to photorefractive holography combined with pulsed ultrasound, we perform a time-resolved detection of ultrasound-modulated photons in the therapeutic window (780 nm). A high-gain SPS:Te crystal is used for this purpose and enables us to image through large optical thickness (500 mean free paths). We are able to generate three-dimensional (3D) acousto-optic images by translating a multielement ultrasound probe in only one direction. A 3D absorbing object is imaged through a 3 cm thick phantom.     

Rheology and Drug Release Properties of Bioresorbable Hydrogels Prepared from Polylactide/Poly(ethylene glycol) Block Copolymers

Ring-opening polymerization of L(D)-lactide was realized in the presence of poly(ethylene glycol) (PEG), yielding PLLA/PEG and PDLA/PEG block copolymers. Bioresorbable hydrogels were prepared from aqueous solutions containing both copolymers due to interactions and stereocomplexation between PLLA and PDLA blocks. The rheological properties of the hydrogels were investigated under various conditions by changing copolymer concentration, temperature, time and frequency. The hydrogels constitute a dynamic and evolutive system because of continuous formation/destruction of crosslinks and degradation. Drug release studies were performed on hydrogel systems containing bovine serum albumin (BSA). The release profiles appear almost constant with little burst effect. The release rate depends not only on gelation conditions such as time and temperature, but also on factors such as drug load, as well as molar mass and concentration of the copolymers.     

Confocal Raman Spectroscopic Imaging for Evaluation of Distribution of Nano-Formulated Hydrophobic Active Cosmetic Ingredients in Hydrophilic Films

Film-forming systems are highly relevant to the topical administration of active ingredients (AI) to the body. Enhanced contact with the skin can increase the efficacy of delivery and penetration during prolonged exposure. However, after the evaporation of volatile solvents to form a thin film, the distribution of the ingredient should remain homogenous in order to ensure the effectiveness of the formula. This is especially critical for the use of hydrophobic molecules that have poor solubility in hydrophilic films. In order to address this concern, hydroxyphenethyl esters (PHE) of Punica granatum seed oil were prepared as a nanosuspension stabilised by poloxamers (NanoPHE). NanoPHE was then added to a formulation containing polyvinyl alcohol (PVA) as a film forming agent, Glycerol as a plasticiser and an antimicrobial agent, Sepicide^TM HB. Despite their reliability, reference methods such as high-performance liquid chromatography are increasingly challenged due to the need for consumables and solvents, which is contrary to current concerns about green industry in the cosmetics field. Moreover, such methods fail to provide spatially resolved chemical information. In order to investigate the distribution of ingredients in the dried film, Confocal Raman imaging (CRI) coupled to Non-negatively Constrained Least Squares (NCLS) analysis was used. The reconstructed heat maps from a range of films containing systematically varying PHE concentrations highlighted the changes in spectral contribution from each of the ingredients. First, using NCLS scores it was demonstrated that the distributions of PVA, Glycerol, Sepicide^TM HB and PHE were homogenous, with respective relative standard deviations (RSD) of 3.33%, 2.48%, 2.72% and 6.27%. Second, the respective relationships between ingredient concentrations in the films and their Raman responses, and the spectral abundance were established. Finally, a model for absolute quantification for PHE was be constructed using the percentage of spectral abundance. The prepared %w/w concentrations regressed against predicted %w/w concentrations, displaying high correlation (R² = 0.995), while the Root Mean Squared Error (0.0869% w/w PHE) confirmed the precision of the analysis. The mean percent relative error of 3.75% indicates the accuracy to which the concentration in dried films could be determined, further supporting the suitability of CRI for analysis of composite solid film matrix. Ultimately, it was demonstrated that nanoformulation of hydrophobic PHE provides homogenous distribution in PVA based film-forming systems independent of the concentration of NanoPHE used in the formula.     

Evaluation of Sample Preparation Methods for Non-Target Screening of Organic Micropollutants in Urban Waters Using High-Resolution Mass Spectrometry

Non-target screening (NTS) has gained interest in recent years for environmental monitoring purposes because it enables the analysis of a large number of pollutants without predefined lists of molecules. However, sample preparation methods are diverse, and few have been systematically compared in terms of the amount and relevance of the information obtained by subsequent NTS analysis. The goal of this work was to compare a large number of sample extraction methods for the unknown screening of urban waters. Various phases were tested for the solid-phase extraction of micropollutants from these waters. The evaluation of the different phases was assessed by statistical analysis based on the number of detected molecules, their range, and physicochemical properties (molecular weight, standard recoveries, polarity, and optical properties). Though each cartridge provided its own advantages, a multilayer cartridge combining several phases gathered more information in one single extraction by benefiting from the specificity of each one of its layers.     

Mannich-Type Reactions of Alkylzinc Reagents

Mannich-type reactions involving alkylzinc reagents have been developed using different strategies. We show that the addition of these organometallic species to sulfonyl imines occurs upon simple heating and affords Mannich products in moderate to excellent yields (14 examples, 30–99 %). Interestingly, N-alkyl imines were also found to be suitable partners after activation as an acyliminium by acetyl chloride (12 examples, 49–86 %) or, more originally, by TMSCl (14 examples, 26–87 %). These methods proved complementary, leading to the preparation of both N-protected secondary or tertiary amines and N-unprotected secondary amines in good yields, with an increased eco-compatibility, and under simple conditions.     

Influence of the Crystallinity of Silver Nanoparticles on Their Magnetic Properties

The magnetic properties of noble-metal nanoparticles are a puzzling phenomenon, tentatively often explained as a size effect or a ligand effect. Many experimental studies performed to date have attempted to vary these readily available parameters without reaching a definitive conclusion. In an attempt at better understanding the role of core crystallinity on these magnetic properties, we have compared the behavior of silver nanoparticles, which were either single-crystalline or multi-twinned, of almost identical sizes and with the same ligand coating. Our results indicate that single-crystalline nanoparticles tend to behave as classical paramagnetic materials, whereas multi-twinned ones exhibit a combination of para- and ferro-magnetic behaviors. Our hypothesis is that lattice defects within the core bear magnetic moments which couple through conduction electrons, with dipolar interactions also playing a local and macroscopic role.     

Sydnone-Cyanines as Clickable Probes for Fluorescent Labelling

The synthesis of four clickable sydnone-heptamethine cyanine derivatives is described in this article. The synthetic route is based on a palladium-cross coupling reactions of sydnone boronates affording the desired sydnone-cyanine conjugates in only five steps. These compounds were shown to react smoothly with cyclooctynes to form the corresponding pyrazoles clicked products quantitatively at room temperature and with rate constants up to 18 m ⁻¹ ⋅ s⁻¹, affording interesting new tools for biorthogonal fluorescent labelling of (bio)molecules. Fluorescence properties of both sydnone- and pyrazole-cyanines are described, as well.