DOPO‐Based Phosphorus‐Containing Methacrylic (Co)Polymers: Glass Transition Temperature Investigation

A two‐step synthetic procedure is designed for preparing new flame‐retardant methacrylic monomers containing 9,10‐dihydro‐9‐oxa‐10‐phosphaphenanthrene‐10‐oxide (DOPO) as a substituent side group. DOPO and methacrylate moieties are linked by linear aliphatic hydrocarbon spacers (3 to 11 carbon atoms). Copolymerization with methyl methacrylate is carried out leading to copolymers containing between 2 and 10 wt% phosphorus. All homo‐ and copolymers exhibit a unique glass transition temperature (T_g ). A new group contribution for DOPO‐based substituent is extracted that leads to reasonable estimations of T_g s of other published polymers. The Fox equation provides a good estimation of T_g s for most copolymers and for physical blends of poly(methyl methacrylate) (PMMA) and DOPO. When using monomers having three and four carbon atoms in the hydrocarbon spacer, the T_g of copolymers remains close to that of PMMA over a wide range of composition.     

Accelerated growth of calcium silicate hydrates: Experiments and simulations

Despite the usefulness of isothermal calorimetry in cement analytics, without any further computations this brings only little information on the nucleation and growth of hydrates. A model originally developed by Garrault et al. is used in this study in order to simulate hydration curves of cement obtained by calorimetry with different known hardening accelerators. The limited basis set of parameters used in this model, having a physical or chemical significance, is valuable for a better understanding of mechanisms underlying in the acceleration of C–S–H precipitation. Alite hydration in presence of four different types of hardening accelerators was investigated. It is evidenced that each accelerator type plays a specific role on one or several growth parameters and that the model may support the development of new accelerators. Those simulations supported by experimental observations enable us to follow the formation of the C–S–H layer around grains and to extract interesting information on its apparent permeability.     

Myo-InositolTrisPyroPhosphate treatment leads to HIF-1α suppression and eradication of early hepatoma tumors in rats

Myo-inositol trispyrophosphate (ITPP), a synthetic allosteric effector of hemoglobin, increases the regulated oxygen-releasing capacity of red blood cells (RBCs), leading to suppression of hypoxia-inducible factor 1α (HIF-1α) and to down-regulation of hypoxia-inducible genes such as vascular endothelial growth factor (VEGF). As a consequence, tumor growth is markedly affected. The effect of weekly intravenous injection of ITPP on an orthotopic, syngenic rat hepatocellular carcinoma (HCC) model was compared to that for untreated animals and animals subjected to conventional Doxorubicin chemotherapy. The longitudinal examination of HCC was performed by microCT imaging, and the cellular and molecular changes were evaluated by histology and Western blotting analysis of HIF-1α, VEGF, and caspase-3 gene expression in the tumor and in the surrounding liver. Hematologic impact was evaluated by blood cell-count measurement and determination of P50 (oxygen partial pressure for a 50 % oxygen saturation of hemoglobin). The HCC evaluation by microCT revealed a high potency of ITPP for tumor growth inhibition, thus allowing long-term survival and even cure of almost all the treated animals. The P50 value of hemoglobin in RBCs underwent a shift of 30 % following ITPP injection. Under these conditions, HIF-1α activity was strongly decreased, VEGF expression was down-regulated, and apoptosis was induced in HCC and surrounding liver cells, as indicated by Caspase-3 expression. ITPP did not affect hematologic parameters during treatment. The observations of in vivo tumor eradication suggest a significant clinical potential for ITPP in cancer therapy.     

Activity-based profiling of retaining β-glucosidases: a comparative study

Activity-based protein profiling (ABPP) is a versatile strategy to report on enzyme activity in vitro, in situ, and in vivo. The development and use of ABPP tools and techniques has met with considerable success in monitoring physiological processes involving esterases and proteases. Activity-based profiling of glycosidases, on the other hand, has proven more difficult, and to date no broad-spectrum glycosidase activity-based probes (ABPs) have been reported. In a comparative study, we investigated both 2-deoxy-2-fluoroglycosides and cyclitol epoxides for their utility as a starting point towards retaining β-glucosidase ABP. We also investigated the merits of direct labeling and two-step bio-orthogonal labeling in reporting on glucosidase activity under various conditions. Our results demonstrate that 1) in general cyclitol epoxides are the superior glucosidase ABPs, 2) that direct labeling is the more efficient approach but it hinges on the ability of the glucosidase to be accommodated in the active site of the reporter (BODIPY) entity, and 3) that two-step bio-orthogonal labeling can be achieved on isolated enzymes but translating this protocol to cell extracts requires more investigation.     

Visualizing biochemical activities in living cells through chemistry

The development of molecular probes to visualize cellular processes is an important challenge in chemical biology. One possibility to create such cellular indicators is based on the selective labeling of proteins with synthetic probes in living cells. Over the last years, our laboratory has developed different labeling approaches for monitoring protein activity and for localizing synthetic probes inside living cells. In this article, we review two of these labeling approaches, the SNAP-tag and CLIP-tag technologies, and their use for studying cellular processes.     

Increasing the thermostability of sucrose phosphorylase by a combination of sequence- and structure-based mutagenesis

Sucrose phosphorylase is a promising biocatalyst for the glycosylation of a wide variety of acceptor molecules, but its low thermostability is a serious drawback for industrial applications. In this work, the stability of the enzyme from Bifidobacterium adolescentis has been significantly improved by a combination of smart and rational mutagenesis. The former consists of substituting the most flexible residues with amino acids that occur more frequently at the corresponding positions in related sequences, while the latter is based on a careful inspection of the enzyme's crystal structure to promote electrostatic interactions. In this way, a variant enzyme could be created that contains six mutations and whose half-life at the industrially relevant temperature of 60 °C has more than doubled compared with the wild-type enzyme. An increased stability in the presence of organic co-solvents could also be observed, although these effects were most noticeable at low temperatures.     

Pullulan–STMP hydrogels: a way to correlate crosslinking mechanism,structure and physicochemical properties

Rheological and swelling properties of hydrogels based on pullulan crosslinked with sodium trimetaphosphate (STMP) are explained according to various polymer and crosslinking agent concentrations using ³¹P-nuclear magnetic resonance study. This method has allowed determining the amount of all the species present in the medium when varying both pullulan and STMP concentrations. We have clearly demonstrated with a good agreement by both ³¹P-NMR and rheology that a critical STMP concentration occurs which is function of pullulan concentration. This typical crosslinking agent concentration delimitates the maximum of gel structure together with the minimum of swelling.     

Thermal and mechanical properties of polypropylene/wood‐flour composites

In this research, polypropylene/wood‐flour composites (WPCs) were blended with different contents of wood and/or maleated polypropylene (MAPP) and clay. We found that the addition of MAPP or clay in the formulation greatly improved the dispersion of the wood fibers in the composite; this suggested that MAPP or clay may have played the role of an adhesion promoter in the WPCs. The results obtained with clay indicate that it also acted as a flame retardant. The thermal tests carried out with the produced samples showed an increased crystallization temperature (T_c), crystallinity, and melting temperature (T_m) with wood loading. The increase of the two former parameters was explained by the incorporation of wood flour, which played the role of nucleating agent and induced the crystallization of the matrix polymer. On the other hand, the T_m increase was ascribed to the insulating properties of wood, which hindered the movement of heat conduction. The effects of UV irradiation on T_m and T_c were also examined. T_c increased with UV exposure time; this implied that UV degradation generated short chains with low molecular weight that could move easily in the bulk of the sample and, thus, catalyze early crystallization. The flexural strength and modulus increased with increasing wood‐flour content. In contrast, the impact strength and tensile strength and strain decreased with increasing wood‐flour content. All of these changes were related to the level of dispersion of the wood flour in the polymeric matrix. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Elaboration and Characterization of Advanced Biobased Polyurethane Foams Presenting Anisotropic Behavior

Biobased and open cell polyurethane (PU) foams are produced from a synthesized sorbitol‐based polyester polyol. Different formulations are developed with various blowing agent systems (chemical vs physical blowing). Synthetized foams are fully characterized and compared. The cell morphology is carefully investigated by tomography and scanning electron microscopy. The chemical nature of the primary compounds, foaming kinetics, density, thermal behavior, and conductivity are fully studied, with also the main transition materials temperatures. It is shown that blowing agents especially impact the foaming kinetics. In the case of chemically blowing foams, higher foaming rate and temperatures are obtained. The mechanical behavior is particularly analyzed using quasi‐static compression tests, according two main axes compared to the rise direction. A direct relationship is observed between the formulation, foam structure, foam morphology, and corresponding mechanical properties. Results clearly highlight unexpected properties of biobased PU foams with unveil anisotropic mechanical properties.