Polymer Cocktail: A Multitask Supported Ionic Liquid‐Like Species to Facilitate Multiple and Consecutive C?C Coupling Reactions

Polymer‐supported ionic liquid‐like species (SILLPs) with different functionalities have been combined to obtain new catalytic systems (polymer cocktail) with improved properties towards their application for C C coupling reactions. The SILLPs have been synthesized in a simple way and combined to play different functions in the reaction medium. Those roles involve simultaneously (or consecutively) their actuation as supported reagents, precatalysts and scavengers of undesired reaction side‐products. The system has been tested by employing three different C C coupling reactions for 8 consecutive cycles. Moreover, different aryl bromides and iodides have proved to be efficiently transformed by the catalytic cocktail. Finally, the Heck reaction has been conducted in continuous‐flow conditions using a packed bed of this polymer cocktail and employing supercritical carbon dioxide (scCO₂) as a solvent, which cannot be carried out with the use of soluble bases as this would lead to the clogging of the reactor. Finally, the SILLPs cocktail enables one to combine different reaction steps and purification in a single vessel, which represents a significant improvement in terms of process intensification and green chemistry. This is particularly true in the case of the use of scCO₂ as this allows the direct production of crude materials not contaminated either by salts or by solvents.     

Impact of microparticles on UV disinfection of indigenous aerobic spores

Numerous studies have shown that the efficacy of ultraviolet (UV) disinfection can be hindered by the presence of particles that can shield microorganisms. The main objective of this study was to determine to what extent natural particulate matter can shield indigenous spores of aerobic spore-forming bacteria (ASFB) from UV rays. The extent of the protective shielding was assessed by comparing the inactivation rates in three water fractions (untreated, dispersed and filtered on an 8 microm membrane) using a collimated beam apparatus with a low-pressure lamp emitting at 254 nm. Levels of inactivation were then related to the distribution and abundance of particles as measured by microflow imaging. Disinfection assays were completed on two source waters of different quality and particle content. A protocol was developed to break down particles and disperse aggregates (addition of 100mg/L of Zwittergent 3-12 and blending at 8000 rpm for 4 min). Particle size distribution (PSD) analysis confirmed a statistically significant decrease in the number of particles for diameter ranges above 5 microm following the dispersion protocol and 8 microm filtration. The fluence required to reach 1-log inactivation of ASFB spores was independent of particle concentration, while that required to reach 2-log inactivation or more was correlated with the concentration of particles larger than 8 microm (R(2)>0.61). Results suggest that natural particulate matter can protect indigenous organisms from UV radiation in waters with elevated particle content, while source water with low particle counts may not be subject to this interference.     

Organic contamination of settled house dust, a review for exposure assessment purposes

People spend a considerable amount of time indoors. As a result, exposure to indoor contaminants is of great concern, notably via settled dust ingestion in particular for infants and toddlers. This paper proposes a critical review on the organic contamination of settled house dust and human exposure over the past 10 years and focused on sources, contaminations and measurement methods (sampling, pretreatment, storage and analysis). As many compounds were identified, arises the question of which ones to consider. Sensitive and selective analytical methods for simultaneous determination of targeted substances should be developed and evaluated. Various methods were described for sampling and sample preparation. Harmonization and standardization are needed to enable comparison of results from similar studies. Finally, an integrated multipollutant and multicompartment (settled dust, suspended particles and air) approach appears essential in order to determine the extent of the threat to public health posed by indoor contaminants.     

New insights into the peculiar behavior of laminar burning velocities of hydrogen–air flames according to pressure and equivalence ratio

Hydrogen is a clean and energetic fuel, and its oxidation mechanism is a subset of the oxidation mechanisms of all hydrocarbons. Therefore, the validation of the available kinetic schemes is of great importance. In the current study, experimental measurements of laminar flame speeds and modeling studies were performed for H₂–air premixed flames over a wide range of equivalence ratios (0.5–4.0) and pressures (0.2–3 bar). The large scale in mixture and thermodynamic conditions allows a better understanding of the peculiar behavior of hydrogen flame speeds with pressure. Two very recent detailed chemical kinetic mechanisms for hydrogen combustion were selected. Excellent agreement was observed between calculations and experimental results, confirming the validity of the kinetic schemes selected. The kinetic analyses performed allow proposing an explanation for the nonmonotonic variation of hydrogen/air flame speed with pressure observed in the experiments.     

Persistent excitation condition within the dual control framework

Model Predictive Control framework is currently used in many different fields of expertise. The inherent part and very often also the main bottleneck is the model of a process used for the computation of predictions.Due to many reasons e.g. ageing, from time to time there exists a need to adjust/re-identify (if there was already some kind of a model-based controller) or to construct a brand new model (in other cases). Frequently, the process generating the data is under some kind of control, imposing thus problems when classical open loop identification methods are considered. The need for models identified from the data gathered in a closed-loop fashion and a request for possible re-identification of the model parameters lead to the emerge of dual control where the problems of control and system identification are addressed simultaneously.In this paper, we present a new algorithm based on the persistent excitation condition when the minimal eigenvalue of the information matrix is maximized in order to have sufficiently exciting optimal control signal satisfying the control requirements.     

A Material Model for TRIP‐Steels and its Application to a CrMnNi Cast Alloy

A material model is presented that accounts for strain rate dependent inelastic deformation and strain‐induced phase transformation in TRIP‐steels. Modifications for the kinetics equations of the strain‐induced phase transformation, introduced by Stringfellow, are proposed to overcome a drawback of Stringfellow's model. A parameter identification strategy that relies on Gauss‐Markov estimates is used to determine the model parameters from experimental data of a recently developed cast TRIP‐steel. Good agreement is observed between experimental results of the compression test and the corresponding finite element simulation employing the proposed model. This forms the basis for future applications of the material model in the design of composites and structures.     

Solitary fibrous tumor of the adrenal gland

Solitary fibrous tumors are rare neoplasms, most commonly involving the pleura, recently described in various other locations. We report a solitary fibrous tumor of the right adrenal gland in a 42-year-old woman, discovered incidentally during abdominopelvic ultrasonographic examination. Pathologic and immunohistologic features of the tumor were identical to those of other solitary fibrous tumors. Three-quarters of this unencapsulated infiltrating tumoral mass presented foci of hemorrhage and were made of small, round, epithelioid-like cells that expressed the CD34 antigen more weakly than do the typical spindle cells usually observed in solitary fibrous tumors. Despite hemorrhage and poor limitation, the tumor behaved in a innocuous manner; the mass remaining unchanged for more than 5 years before the patient agreed to surgical intervention, which was recommended because of a sudden enlargement of the mass.     

Homocamptothecins: synthesis and antitumor activity of novel E-ring-modified camptothecin analogues

Homocamptothecin (hCPT), a camptothecin (CPT) analogue with a seven membered beta-hydroxylactone which combines enhanced plasma stability and potent topoisomerase I (Topo I)-mediated activity, is an attractive template for the elaboration of new anticancer agents. Like CPT, hCPT carries an asymmetric tertiary alcohol and displays stereoselective inhibition of Topo I. The preparation and biological screening of racemic hCPT analogues are described. The 10 hCPTs tested were better Topo I inhibitors than CPT. Fluorinated hCPTs 23c, d,f,g were found to have potent cytotoxic activity on A427 and PC-3 tumor cell lines. Their cytotoxicity remained high on the K562adr and MCF7mdr cell lines, which overexpress a functionally active P-glycoprotein. Fluorinated hCPTs were more efficacious in vivo than CPT on HT-29 xenografts. In this model, a tumor growth delay of 25 days was reached with hCPT 23g at a daily dose of 0.32 mg/kg, compared to 4 days with CPT at 0.625 mg/kg. Thus difluorinated hCPT 23g warrants further investigation as a novel Topo I inhibitor with high cytotoxicity toward tumor cells and promising in vivo efficacy.