Predicting the phase equilibria of synthetic petroleum fluids with the PPR78 approach

The PPR78 approach is a group contribution‐based thermodynamic model which combines at constant packing fraction the Peng–Robinson equation of state and a Van Laar‐type g^E model. This article demonstrates that, using classical mixing rules (linear on b and quadratic on a), the PPR78 model may also be seen as a group contribution method for the estimation of the temperature‐dependent k_ij of the widely used PR EoS. Our model is endowed of 15 groups and it is possible to predict the k_ij for any mixture containing alkanes, aromatics, naphthenes, CO₂, N₂, H₂S, and mercaptans. This study exhibits the capability of this approach to predict the phase behavior of synthetic petroleum fluids containing components of different volatilities. The many comparisons between calculated and experimental data on natural gases, crude oils, and gas condensates allow concluding that the PPR78 approach is a successful model for phase equilibria calculations of this kind of mixtures. © 2010 American Institute of Chemical Engineers AIChE J, 2010     

Dendrimer intercalation in layered double hydroxides

New organic/inorganic (O/I) hybrid assemblies based on Layered Double Hydroxide (LDH) with polyamide amine dendrimer (PAMAM, generation −0.5 and generation +0.5) were prepared by two different routes using either the direct coprecipitation at constant pH or the anion exchange procedure in double surfactant S⁺S⁻ phases. The obtained materials were characterized by means of powder X-ray diffraction, thermal gravimetric analysis associated with mass spectrometry, and Fourier-transform infrared spectroscopy. X-ray powder diffraction pattern of the O/I LDH assembly exhibit characteristic profiles of LDH-based materials with basal spacing depending on the nature of the dendrimer. Indeed, for both synthetic procedures, interleaved PAMAM −0.5 gives rise to an interlayer space in agreement with a perpendicular molecular arrangement against the layer of the host structure. For PAMAM+0.5, considering its spherical dimension, a much smaller basal spacing was observed. This observation was interpreted as shrinkage of the molecule to accommodate the interlayer LDH gap, which was rendered possible by the bond angle twisting within PAMAM−0.5. FTIR spectra confirm the presence of both moieties inside both Zn₂Al/PAMAM G−0.5 and Zn₂Al/PAMAM G+0.5 assemblies. Finally, thermal analysis associated with mass spectrometry confirm this composition, and in situ temperature XRD data reveal that the highly constrained arrangement for the generation +0.5 is not accompanied by a gain in thermal structural stability; in fact, the assembly prepared from PAMAM −0.5 is more stable. Both O/I PAMAM LDH assemblies constitute well-defined materials which are candidate for catalytic applications.     

Design,Synthesis and Evaluation of a Series of 1,5-Diaryl-1,2,3-triazole-4-carbohydrazones as Inhibitors of the YAP-TAZ/TEAD Complex

Starting from our previously reported hit, a series of 1,5-diaryl-1,2,3-triazole-4-carbohydrazones were synthesized and evaluated as inhibitors of the YAP/TAZ-TEAD complex. Their binding to hTEAD2 was confirmed by nanodifferential scanning fluorimetry, and some of the compounds were also found to moderately disrupt the YAP-TEAD interaction, as assessed by a fluorescence polarization assay. A TEAD luciferase gene reporter assay performed in HEK293T cells and RTqPCR measurements in MDA-MB231 cells showed that these compounds inhibit YAP/TAZ-TEAD activity to cells in the micromolar range. In spite of the cytotoxic effects displayed by some of the compounds of this series, they are still good starting points and can be suitably modified into an effective and viable YAP-TEAD disruptor in the future.     

Polyoxometalates/polymer composites for the photodegradation of bisphenol-A

Nowadays water scarcity represents a threat for human and living beings. Therefore, to satisfy the demands of people for clean and safe water, new technologies for wastewater treatment have been developed. Thus, photocatalysis has emerged as a green chemical approach for such treatment. In this context, new polyoxometalate (POM)/polymer composites with relevant photocatalytic properties have been developed via an easy and cheap photopolymerization process upon mild visible light irradiation at 405 nm. This fruitful association between POM and polymer allowed the obtention of shaped materials facile to collect and reuse at the end of the photocatalytic treatment avoiding then the usual time-consuming regeneration methods. The prepared photocomposites displayed excellent photocatalytic performance for the removal of bisphenol-A from water under different sources of irradiation. Hence, 100%, 88%, and 50% of this model compound were decomposed by the phosphomolybdic composite under just 90 min of UV lamp, solar and LED@375 nm irradiations, respectively. The effectiveness of these developed photocatalysts towards the degradation of other organic compounds, as well as the degradation mechanism based on the generation of highly reactive chemicals such as ^•OH radicals promoting the degradation were already reported. Bisphenol-A degradation pathway and the identification of the photoproducts were discussed using mass spectroscopy technique. Therefore, this paper highlighted the photocatalytic efficiency of the new manufactured materials for the photodegradation of the bisphenol-A, thus expanding their application fields, under different sources of irradiation and under pure solar irradiation which make their applications more interesting and less energy consuming.     

Advanced burner-rig test for oxidation-corrosion resistance evaluation of MCrAlY/superalloys systems

Protective coatings are used on gas turbine components to enable them to survive in engine-operating conditions. This study presents a recently developed cyclic burner-rig test that is used to simulate helicopter engine conditions and to assess the oxidation and hot corrosion behaviour of MCrAlY coatings on nickel-base superalloys. A diluted sea-salt solution is atomised into the burner-rig to simulate hot-corrosion. Each cycle lasts 1 h with temperatures varying in the range of 900 °C to 1000 °C followed by 15 min cooling to room temperature. Specimens are tested up to 1000 such cycles. Three different NiCoCrAlYTa coating thicknesses are used to determine the influence of the Al reservoir on the lifetime of the coated MC2 superalloy. The evolving microstructural features are identified using high resolution scanning electron microscopy and energy dispersive spectroscopy and compared with isothermal testing in pure oxidising conditions. The NiCoCrAlYTa microstructure obtained after the burner-rig test has typical features of a Type 1 hot corrosion degradation, with internal oxidation and nitruration and a front of chromium and yttrium-rich sulphides. This type of advanced burner-rig test cycle is successful in reproducing the accelerated combined hot-corrosion/oxidation damage.     

Coal pyrolysis in a rotary kiln: Part I. Model of the pyrolysis of a single grain

A mathematical model is presented which describes the pyrolysis of a single grain of coal and is designed to be incorporated into an overall model simulating the rotary kiln coal pyrolysis process. The grain model takes into account the principal physical phenomena occurring during the conversion of coal to coke, namely, heat transfer toward and within the grain, drying of the coal, and the evolution of volatile species. Particular care has been taken in the determination of the thermophysical and kinetic parameters necessary for the model. Thus, the drying kinetics for Lorraine coal were measured by thermogravimetry. The kinetics of pyrolysis were determined by both thermogravimetry and gasphase chromatography, in order to separately monitor the evolution of the nine gaseous species considered. The true specific heat and the thermal conductivity of the solid were also measured as a function of temperature. The numerical model, based on the finite-volume method, calculates the temperature, composition, and mass flow rates for the different gases evolved at each point in the grain at any instant of time. The model was, finally, validated by comparing the calculated and measured values of the overall conversion of the pyrolysis reaction and the temperature at the center of the grain.     

Molecular Liver Fingerprint Reflects the Seasonal Physiology of the Grey Mouse Lemur (Microcebus murinus) during Winter

Grey mouse lemurs (Microcebus murinus) are primates that respond to environmental energetic constraints through strong physiological seasonality. They notably fatten during early winter (EW), and mobilize their lipid reserves while developing glucose intolerance during late winter (LW), when food availability is low. To decipher how the hepatic mechanisms may support such metabolic flexibility, we analyzed the liver proteome of adult captive male mouse lemurs, whose seasonal regulations are comparable to their wild counterparts. We highlight profound hepatic changes that reflect fat accretion in EW at the whole-body level, without triggering an ectopic storage of fat in the liver, however. Moreover, molecular regulations are consistent with the decrease in liver glucose utilization in LW, and therefore with reduced tolerance to glucose. However, no major regulation was seen in insulin signaling/resistance pathways. Fat mobilization in LW appeared possibly linked to the reactivation of the reproductive system while enhanced liver detoxification may reflect an anticipation to return to summer levels of food intake. Overall, these results show that the physiology of mouse lemurs during winter relies on solid molecular foundations in liver processes to adapt fuel partitioning while opposing the development of a pathological state despite large lipid fluxes.     

Bone Marrow MSC Secretome Increases Equine Articular Chondrocyte Collagen Accumulation and Their Migratory Capacities

Equine osteoarthritis (OA) leads to cartilage degradation with impaired animal well-being, premature cessation of sport activity, and financial losses. Mesenchymal stem cell (MSC)-based therapies are promising for cartilage repair, but face limitations inherent to the cell itself. Soluble mediators and extracellular vesicles (EVs) secreted by MSCs are the alternatives to overcome those limitations while preserving MSC restorative properties. The effect of equine bone marrow MSC secretome on equine articular chondrocytes (eACs) was analyzed with indirect co-culture and/or MSC-conditioned media (CM). The expression of healthy cartilage/OA and proliferation markers was evaluated in eACs (monolayers or organoids). In vitro repair experiments with MSC-CM were made to evaluate the proliferation and migration of eACs. The presence of nanosized EVs in MSC-CM was appraised with nanoparticle tracking assay and transmission electron microscopy. Our results demonstrated that the MSC secretome influences eAC phenotype by increasing cartilage functionality markers and cell migration in a greater way than MSCs, which could delay OA final outcomes. This study makes acellular therapy an appealing strategy to improve equine OA treatments. However, the MSC secretome contains a wide variety of soluble mediators and small EVs, such as exosomes, and further investigation must be performed to understand the mechanisms occurring behind these promising effects.     

Morphological and Mechanical Characterization of Extracellular Vesicles and Parent Human Synoviocytes under Physiological and Inflammatory Conditions

The morphology of fibroblast-like synoviocytes (FLS) issued from the synovial fluid (SF) of patients suffering from osteoarthritis (OA), rheumatoid arthritis (RA), or from healthy subjects (H), as well as the ultrastructure and mechanical properties of the FLS-secreted extracellular vesicles (EV), were analyzed by confocal microscopy, transmission electron microscopy, atomic force microscopy, and tribological tests. EV released under healthy conditions were constituted of several lipid bilayers surrounding a viscous inner core. This “gel-in” vesicular structure ensured high mechanical resistance of single vesicles and good tribological properties of the lubricant. RA, and to a lesser extent OA, synovial vesicles had altered morphology, corresponding to a “gel-out” situation with vesicles surrounded by a viscous gel, poor mechanical resistance, and poor lubricating qualities. When subjected to inflammatory conditions, healthy cells developed phenotypes similar to that of RA samples, which reinforces the importance of inflammatory processes in the loss of lubricating properties of SF.     

Immunothrombosis and the Role of Platelets in Venous Thromboembolic Diseases

Venous thromboembolism (VTE) is the third leading cardiovascular cause of death and is conventionally treated with anticoagulants that directly antagonize coagulation. However, recent data have demonstrated that also platelets play a crucial role in VTE pathophysiology. In the current review, we outline how platelets are involved during all stages of experimental venous thrombosis. Platelets mediate initiation of the disease by attaching to the vessel wall upon which they mediate leukocyte recruitment. This process is referred to as immunothrombosis, and within this novel concept inflammatory cells such as leukocytes and platelets directly drive the progression of VTE. In addition to their involvement in immunothrombosis, activated platelets can directly drive venous thrombosis by supporting coagulation and secreting procoagulant factors. Furthermore, fibrinolysis and vessel resolution are (partly) mediated by platelets. Finally, we summarize how conventional antiplatelet therapy can prevent experimental venous thrombosis and impacts (recurrent) VTE in humans.