New phospholipid fatty acids from the marine spongeCinachyrella alloclada uliczka

The fatty acid composition of phospholipids from the Senegalese spongeCinachyrella alloclada was examined. Two new fatty acids not hitherto found in nature, namely 10,13-octadecadienoic acid and 16-tricosenoic acid, were identified. 8-Hexadecenoic, 13-nonadecenoic and 5,9,13-trimethyltretradecanoic fatty acids were also found for the first time in sponges. The latter compound (1.4% of the total fatty acid mixture), an isoprenoid fatty acid, accompanies the major fatty acid 4,8,12-trimethyltridecanoic acid (19.7%). The monomethyl branched fatty acids (22%) identified include 23-methylpentacosanoic acid (anteiso-26∶0), not previously observed in sponged. The major long-chain fatty acids encountered were the known 17-tetracosenoic 19-heptacosadienoic and 5,9,23-tricontatrienoic acid. Some sixty fatty acids were identified as methyl esters andN-acyl pyrrolidides by gas chromatography and gas chromatography/mass spectrometry.     

Thioether Analogues of Disulfide‐Bridged Cyclic Peptides Targeting Death Receptor 5: Conformational Analysis,Dimerisation and Consequences for Receptor Activation

Cyclic peptides containing redox‐stable thioether bridges might provide a useful alternative to disulfide‐bridged bioactive peptides. We report the effect of replacing the disulfide bridge with a lanthionine linkage in a 16‐mer cyclic peptide that binds to death receptor 5 (DR5, TRAIL‐R2). Upon covalent oligomerisation, the disulfide‐bridged peptide has previously shown similar behaviour to that of TNF‐related apoptosis inducing ligand (TRAIL), by selectively triggering the DR5 cell death pathway. The structural and biological properties of the DR5‐binding peptide and its desulfurised analogue were compared. Surface plasmon resonance (SPR) data suggest that these peptides bind DR5 with comparable affinities. The same holds true for dimeric versions of these peptides: the thioether is able to induce DR5‐mediated apoptosis of BJAB lymphoma and tumorigenic BJELR cells, albeit to a slightly lower extent compared to its disulfide homologue. NMR analysis revealed subtle variation in the conformations of the two peptides and suggests that the thioether peptide is slightly less folded than its disulfide homologue. These observations could account for the different capability of the two dimers to cluster DR5 receptors on the cell surface and to trigger apoptosis. Nevertheless, our results suggest that the thioether peptide is a potential candidate for evaluation in animal models.     

Fast Measurements of the Gas‐Liquid Diffusion Coefficient in the Gaussian Wake of a Spherical Bubble

A fast method is proposed for determining the oxygen gas‐liquid diffusion coefficient from measurements of the fluorescence quenching behind a bubble. The approach consists of capturing pictures of the concentration field at micro‐scale in the laminar bubble wake. The Gaussian concentration profiles measured in the wake are demonstrated to be systematically equivalent to an instantaneous plane diffusion case. The approach permits to accurately evaluate the gas‐liquid diffusivity in a very short time of around one second.     

Chemical Defenses of the Sacoglossan Mollusk Elysia rufescens and Its Host Alga Bryopsis sp.

Sacoglossans are a group of opisthobranch mollusks that have been the source of numerous secondary metabolites; however, there are few examples where a defensive ecological role for these compounds has been demonstrated experimentally. We investigated the deterrent properties of the sacoglossan Elysia rufescens and its food alga Bryopsis sp. against natural fish predators. Bryopsis sp. produces kahalalide F, a major depsipeptide that is accumulated by the sacoglossan and that shows in vitro cytotoxicity against several cancer cell lines. Our data show that both Bryopsis sp. and Elysia rufescens are chemically protected against fish predators, as indicated by the deterrent properties of their extracts at naturally occurring concentrations. Following bioassay-guided fractionation, we observed that the antipredatory compounds of Bryopsis sp. were present in the butanol and chloroform fractions, both containing the depsipeptide kahalalide F. Antipredatory compounds of Elysia rufescens were exclusively present in the dichloromethane fraction. Further bioassay-guided fractionation led to the isolation of kahalalide F as the only compound responsible for the deterrent properties of the sacoglossan. Our data show that kahalalide F protects both Bryopsis sp. and Elysia rufescens from fish predation. This is the first report of a diet-derived depsipeptide used as a chemical defense in a sacoglossan.     

Mechanical Properties of an Extruded Wood Plastic Composite: Analytical Modeling

Abstract

The focus of this study has been to predict wood plastic composite (WPC) properties using analytical models dedicated to reinforced composites and to define their limits. Experiment tests have been realized to characterize mechanical properties of a commercial WPC. On one hand, good compressive and three points bending performances were observed in agreement with application requirements for this decking product. On the other hand, lower tensile performance and failure appearances revealed a lack of interfacial bonding between wood fiber and matrix despite the presence of a coupling agent in the composite formulation.     

In‐line monitoring of the injection molding process by dielectric spectroscopy

In recent years, electrical techniques like microdielectrometry have increasingly been utilized for their ability to continuously monitor, in a nondestructive way, the advancement of the reaction of thermoset resins under cure. This paper discusses an extension of this technique for the “in‐situ” monitoring of the crystallization of thermoplastics applied during an injection molding process. Electric sensors were positioned at the walls of the mold cavity so that an analysis of the volume dielectric properties of material during the filling, the post‐filling, and the cooling steps could be carried out. Poly(vinylidene fluoride) was chosen for this study. A correlation between the evolution of the dielectric parameters and the succession of the steps in this process was undertaken. The dielectric response was sufficiently sensitive to identify the steps of the closing of the mold, filling, post‐filling, cooling, and ejection of the part. In addition, information concerning the crystallization phenomenon near the wall or in the middle of the sample was collected. The gradual filling of the cavity of the mold was also identified by dielectric measurements. The temperature dependence of dielectric properties of the sample was beneficial in evaluating the increase of the temperature of the mold with the succession of injection cycles. The influence of the packing pressure has been clearly identified and confirms the usefulness of the dielectric method as a probe for detecting the shrinkage of the part during the optimization phase of the machine parameters. The dielectric method detailed herein provides a new non‐invasive technique and could be applied to a closed‐loop control of the injection molding process.     

Rapid Discrimination of Neuromyelitis Optica Spectrum Disorder and Multiple Sclerosis Using Machine Learning on Infrared Spectra of Sera

Neuromyelitis optica spectrum disorder (NMOSD) and multiple sclerosis (MS) are both autoimmune inflammatory and demyelinating diseases of the central nervous system. NMOSD is a highly disabling disease and rapid introduction of the appropriate treatment at the acute phase is crucial to prevent sequelae. Specific criteria were established in 2015 and provide keys to distinguish NMOSD and MS. One of the most reliable criteria for NMOSD diagnosis is detection in patient’s serum of an antibody that attacks the water channel aquaporin-4 (AQP-4). Another target in NMOSD is myelin oligodendrocyte glycoprotein (MOG), delineating a new spectrum of diseases called MOG-associated diseases. Lastly, patients with NMOSD can be negative for both AQP-4 and MOG antibodies. At disease onset, NMOSD symptoms are very similar to MS symptoms from a clinical and radiological perspective. Thus, at first episode, given the urgency of starting the anti-inflammatory treatment, there is an unmet need to differentiate NMOSD subtypes from MS. Here, we used Fourier transform infrared spectroscopy in combination with a machine learning algorithm with the aim of distinguishing the infrared signatures of sera of a first episode of NMOSD from those of a first episode of relapsing-remitting MS, as well as from those of healthy subjects and patients with chronic inflammatory demyelinating polyneuropathy. Our results showed that NMOSD patients were distinguished from MS patients and healthy subjects with a sensitivity of 100% and a specificity of 100%. We also discuss the distinction between the different NMOSD serostatuses. The coupling of infrared spectroscopy of sera to machine learning is a promising cost-effective, rapid and reliable differential diagnosis tool capable of helping to gain valuable time in patients’ treatment.     

Hydrothermal preparation of nanotubular particles of a 1:1 nickel phyllosilicate

Hydrothermal treatment of a mixture of nickel chloride, silicic acid and sodium hydroxide at a relatively low temperature, 250 °C and pressure, 10 MPa gave a 1:1 nickel phyllosilicate, [Ni₃Si₂O₅(OH)₄] composed exclusively of hollow, open ended, multiwall nanotubular particles, up to 200 nm in length. No other phases, in particular no silicate platelets were seen. Previous reports on the hydrothermal preparation of tubular nickel phyllosilicate emphasized the need for high temperatures and pressures (ca 400 °C and 70 MPa), with lower temperature giving mostly small thin plate-like products. The tubular particles obtained also had larger outer diameters, 25–30 nm, and larger inner hollow cores, about 10 nm in diameter than nickel silicate nanotubes prepared at high temperatures and pressures. The XRD pattern of the product matched that of pecoraite, the nickel analogue of the tubular magnesium silicate mineral chrysotile. N₂-sorptometry showed the product was mesoporous with a broad range of pore sizes centred around 170 Å, and a BET surface area of 110 m²/g.