Role of phenolic derivatives in photopolymerization of an acrylate coating

The photopolymerization of acrylate resins on wood surfaces suffers from retardation and inhibition effects due to the phenolic derivatives present at the interface. This article details the study of the effect of a set of phenolic compounds on the initiation step. The global effect was recorded by differential scanning calorimetry and photocalorimetry. A comparison between a direct photocleavable initiator such as 2,2‐dimethyloxy‐2‐phenylacetophenone (DMPA) and a two‐component system like benzophenone/N‐methyldiethanolamine (BP/MDEA) suggests that the retardation effect observed in the latter case is due to the interaction between phenols and the triplet state of BP. Subsequently, nanosecond transient absorption (NTA) spectroscopy was used to measure in acetonitrile the quenching rate constants k_Q. A hydrogen abstraction occurred, and the ketyl radical quantum yield was also determined by NTA experiments. In comparison with the photoreduction mechanisms proposed in the literature, the high k_Q values obtained were tentatively correlated to the half‐wave oxidation potentials of phenols in order to discuss the involvement of an electron transfer within the reaction. Some EPR experiments were done to confirm in situ the photoreduction process at the wood surface and the creation of phenoxyl radicals. The interaction of phenols with some initiating radicals was also studied. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 78: 2061–2074, 2000     

New segmented polyurethane ureas based on 4,4′-dicyclohexylmethane diisocyanate and on various soft segments

Linear segmented polyurethane ureas were prepared from 4,4′-dicyclohexylmethane diisocyanate (H₁₂MDI), 4,4′-diamino-3,3′-dicyclohexyl methane (3DCM), and various hydrophilic and hydrophobic soft segments. Kinetic studies of the synthesis of the diisocyanate-terminated prepolymers revealed that the use of too little reactive polyols (that is, polyoxypropylene that bears secondary hydroxyls) could be rather tricky; the noncatalyzed reaction is very slow, but the use of a catalyst soon triggers the formation of side products, and the processing window consequently becomes quite short. Microcalorimetric and dynamic mechanical measurements showed that all the materials were highly phase-segregated elastomers and displayed good mechanical properties up to high temperature (typically 180°C), provided that they had been postcured properly; in this respect, the dramatic effects of isolated (nonchemically linked) hard segments, as well as of too low postcuring temperatures, were demonstrated. Polyurethane ureas compare well with polyureas, and their synthesis can be a good way to cope with the lack of well-adapted commercial diamino-terminated prepolymers. © 1998 John Wiley & Sons, Inc. J Appl Polym Sci 70: 2331–2342, 1998     

Constitutive,Basal, and β-Alanine-Mediated Activation of the Human Mas-Related G Protein-Coupled Receptor D Induces Release of the Inflammatory Cytokine IL-6 and Is Dependent on NF-κB Signaling

G protein-coupled receptors (GPCRs) have emerged as key players in regulating (patho)physiological processes, including inflammation. Members of the Mas-related G protein coupled receptors (MRGPRs), a subfamily of GPCRs, are largely expressed by sensory neurons and known to modulate itch and pain. Several members of MRGPRs are also expressed in mast cells, macrophages, and in cardiovascular tissue, linking them to pseudo-allergic drug reactions and suggesting a pivotal role in the cardiovascular system. However, involvement of the human Mas-related G-protein coupled receptor D (MRGPRD) in the regulation of the inflammatory mediator interleukin 6 (IL-6) has not been demonstrated to date. By stimulating human MRGPRD-expressing HeLa cells with the agonist β-alanine, we observed a release of IL-6. β-alanine-induced signaling through MRGPRD was investigated further by probing downstream signaling effectors along the Gαq/Phospholipase C (PLC) pathway, which results in an IkB kinases (IKK)-mediated canonical activation of nuclear factor kappa-B (NF-κB) and stimulation of IL-6 release. This IL-6 release could be blocked by a Gαq inhibitor (YM-254890), an IKK complex inhibitor (IKK-16), and partly by a PLC inhibitor (U-73122). Additionally, we investigated the constitutive (ligand-independent) and basal activity of MRGPRD and concluded that the observed basal activity of MRGPRD is dependent on the presence of fetal bovine serum (FBS) in the culture medium. Consequently, the dynamic range for IL-6 detection as an assay for β-alanine-mediated activation of MRGPRD is substantially increased by culturing the cells in FBS free medium before treatment. Overall, the observation that MRGPRD mediates the release of IL-6 in an in vitro system, hints at a role as an inflammatory mediator and supports the notion that IL-6 can be used as a marker for MRGPRD activation in an in vitro drug screening assay.     

Second-Generation CD73 Inhibitors Based on a 4,6-Biaryl-2-thiopyridine Scaffold

Various series of 4,6-biaryl-2-thiopyridine derivatives were synthesized and evaluated as potential ecto-5′-nucleotidase (CD73) inhibitors. Two synthetic routes were explored and the coupling of 4,6-disubstituted 3-cyano-2-chloro-pyridines with selected thiols allowed us to explore the structural diversity. Somehow divergent results were obtained in biological assays on CD73 inhibition using either the purified recombinant protein or cell-based assays, highlighting the difficulty to target protein-protein interface on proteins existing as soluble and membrane-bound forms. Among the 18 new derivatives obtained, three derivatives incorporating morpholino substituents on the 4,6-biaryl-2-thiopyridine core were shown to be able to reverse the adenosine-mediated immune suppression on human T cells. The higher blockade efficiency was observed for 2-((3-cyano-4,6-bis(4-morpholinophenyl)pyridin-2-yl)thio)-N-(isoxazol-3-yl)acetamide (with total reversion at 100 μM) and methyl 2-((3-cyano-4,6-bis(4-morpholinophenyl)pyridin-2-yl)thio)acetate (with partial reversion at 10 μM). Thus, this series of compounds illustrates a new chemotype of CD73 allosteric inhibitors.     

Resilient control of cyber-physical systems using adaptive super-twisting observer

In this work, the problem of online secure state estimation and attack reconstruction in the face of offensives that corrupt the sensor measurements and modify the actuator commands of cyber–physical systems is investigated for designing a resilient controller for the system. The states of cyber–physical system and its actuator attacks are estimated/reconstructed online using a novel adaptive line-by-line super-twisting observer, whereas sparse stealth attacks on unprotected sensors are reconstructed using a sparse recovery algorithm. The estimated attacks are used for attack compensation by a resilient controller. The efficacy of the proposed technique is illustrated via simulation on a real electric power system under deception actuator attack and stealth sensor attack.