Pediatric Celiac Disease Patients Show Alterations of Dendritic Cell Shape and Actin Rearrangement

Celiac disease (CD) is a frequent intestinal inflammatory disease occurring in genetically susceptible individuals upon gluten ingestion. Recent studies point to a role in CD for genes involved in cell shape, adhesion and actin rearrangements, including a Rho family regulator, Rho GTPase-activating protein 31 (ARHGAP31). In this study, we investigated the morphology and actin cytoskeletons of peripheral monocyte-derived dendritic cells (DCs) from children with CD and controls when in contact with a physiological substrate, fibronectin. DCs were generated from peripheral blood monocytes of pediatric CD patients and controls. After adhesion on fibronectin, DCs showed a higher number of protrusions and a more elongated shape in CD patients compared with controls, as assessed by immunofluorescence actin staining, transmitted light staining and video time-lapse microscopy. These alterations did not depend on active intestinal inflammation associated with gluten consumption and were specific to CD, since they were not found in subjects affected by other intestinal inflammatory conditions. The elongated morphology was not a result of differences in DC activation or maturation status, and did not depend on the human leukocyte antigen (HLA)-DQ2 haplotype. Notably, we found that ARH-GAP31 mRNA levels were decreased while RhoA-GTP activity was increased in CD DCs, pointing to an impairment of the Rho pathway in CD cells. Accordingly, Rho inhibition was able to prevent the cytoskeleton rearrangements leading to the elongated morphology of celiac DCs upon adhesion on fibronectin, confirming the role of this pathway in the observed phenotype. In conclusion, adhesion on fibronectin discriminated CD from the controls’ DCs, revealing a gluten-independent CD-specific cellular phenotype related to DC shape and regulated by RhoA activity.     

Polymer-derived silicon nitride aerogels as shape stabilizers for low and high-temperature thermal energy storage

This work presents a new skeleton material for thermal energy storage (TES), a silicon nitride aerogel obtained through the pyrolysis of a pre-ceramic polymer. Silicon nitride offers a good combination of thermal conductivity, high-temperature resistance, and chemical inertness. The aerogel porosity can be spontaneously infiltrated with molten NaNO₃, which is a typical phase change material (PCM) in high-temperature TES. The Si₃N₄/NaNO₃ composite exhibits excellent thermal properties with a thermal energy storage efficiency of 82 %, a limited molten salt leakage, and good stability to thermal cycling. The aerogel withstands oxidation up to high temperature and is chemically inert even in contact with salts. This novel aerogel shows also a notable paraffin absorption ability (used in room temperature TES) with negligible leakage even when in contact with absorbent paper. The so-obtained composite reached ≈ 82.4 vol % of organic PCM and a thermal energy storage efficiency of ≈ 62 % compared to neat paraffin.     

On the pyrolysis of a methyl-silsesquioxane in reactive CO2 atmosphere: A TG/MS and FT-IR study

Polymer-derived SiOC-C composites are typically obtained through pyrolysis of a polysiloxane precursor in inert atmosphere. Recent studies have shown that novel SiOC microstructures and compositions can be obtained when the pyrolysis is carried out in a reactive environment, as CO₂, which leads to a selective oxidation of the Si─C bonds leaving a microstructure constituted by a nano-dispersed sp² carbon phase within an SiO₂ matrix. However, little is known about the reaction mechanisms between CO₂ and the preceramic polymer to date. In this work, we investigated the pyrolysis of a methyl-silsesquioxane in reactive (CO₂) and inert (Ar or He) atmosphere by combining TG/MS and FT-IR analysis. The results showed that CO₂ starts to react with the preceramic polymer from ≈750°C when the Si─CH₃ groups start to form Si─CH_x-Si units. The reaction breaks the Si─C bond increasing the amount of the free carbon phase and releasing water vapor, detected by MS, even at temperatures exceeding 900°C. At higher temperatures (≈950°C), CO₂ reacts with the free carbon phase leading to a weight loss and the formation of CO.     

Rate‐dependent self‐healing behavior of an ethylene‐co‐methacrylic acid ionomer under high‐energy impact conditions

In this work, the mechanical and the self‐healing behaviors of an ethylene‐co‐methacrylic acid ionomer were investigated in different testing conditions. The self‐healing capability was explored by ballistic impact tests at low‐velocity, midvelocity, and hypervelocity bullet speed; different experimental conditions such as sample thickness and bullet diameter were examined; in all impact tests, spherical projectiles were used. These experiments, in particular those at low and midspeed, allowed to define a critical ratio between sample thickness and bullet diameter below which full repair was not observed. After ballistic damage, the healing efficiency was evaluated by applying a pressure gradient through tested samples. Subsequently, morphology analysis of the affected areas was made observing all tested samples by scanning electron microscope. This analysis revealed different characteristic features of the damaged zones affected at different projectile speed. Stress–strain curves in uniaxial tension performed at different temperatures and strain rates revealed yield strength and postyield behavior significantly affected by these two parameters. A rise of temperature during high strain rate tests in the viscoplastic deformation region was also detected. This behavior has a strong influence on the self‐repairing mechanism exhibited by the studied material during high‐energy impact tests. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 130: 1949–1958, 2013     

Missing Pieces in Structure Puzzles: How Hyperpolarized NMR Spectroscopy Can Complement Structural Biology and Biochemistry

Structure determination lies at the heart of many biochemical research programs. However, the “giants”: X-ray diffraction, electron microscopy, molecular dynamics simulations, and nuclear magnetic resonance, among others, leave quite a few dark spots on the structural pictures drawn of proteins, nucleic acids, membranes, and other biomacromolecules. For example, structural models under physiological conditions or of short-lived intermediates often remain out of reach of the established experimental methods. This account frames the possibility of including hyperpolarized, that is, dramatically signal-enhanced NMR in existing workflows to fill these spots with detailed depictions. We highlight how integrating methods based on dissolution dynamic nuclear polarization can provide valuable complementary information about formerly inaccessible conformational spaces for many systems. A particular focus will be on hyperpolarized buffers to facilitate the NMR structure determination of challenging systems.     

Processing of polymer-derived,aerogel-filled,SiC foams for high-temperature insulation

Porous polymer-derived ceramics (PDCs) are outperforming materials when low-density and thermal inertia are required. In this frame, thermal insulating foams such as silicon carbide (SiC) ones possess intriguing requisites for aerospace applications, but their thermal conductivity is affected by gas phase heat transfer and, in the high temperature region, by radiative mechanisms. Owing to the versatility of the PDC route, we present a synthesis pathway to embed PDC SiC aerogels within the open cells of a SiC foam, thus sensibly decreasing the thermal conductivity at 1000°C from 0.371 W·m⁻¹K⁻¹ to 0.243 W·m⁻¹K⁻¹. In this way, it was possible to couple the mechanical properties of the foam with the insulating ability of the aerogels. The presented synthesis was optimized by selecting, among acetone, n-hexane, and cyclohexane, the proper solvent for the gelation step of the aerogel formation to obtain a proper mesoporous colloidal structure that, after ceramization at 1000°C, presents a specific surface area of 193 m²·g⁻¹. The so-obtained ceramic composites present a lowest density of 0.18 g·cm⁻³, a porosity of 90% and a compressive strength of 0.76 MPa.     

Low-temperature thermal energy storage with polymer-derived ceramic aerogels

Thermal energy storage (TES) with phase change materials (PCMs) presents some advantages when shape-stabilization is performed with ceramic aerogels. These low-density and ultra-porous materials guarantee high energy density and can be easily regenerated through simple pyrolysis while accounting for moderate mechanical properties. However, the small pore size that typically characterizes these sorbents can hinder the crystallization of PCMs, slightly reducing the energy density of the stabilized compound. In this work, we present the use of polymer-derived mesoporous SiC and SiOC aerogels for the stabilization of polyethylene glycol and a fatty alcohol (PureTemp 23), having a melting temperature of 17 and 23°C, respectively. Their TES performances point out maximum thermal efficiency values of around 80%. These performances are discussed accounting for the results of thermogravimetric analysis, differential scanning calorimetry, and leaking tests.     

Functionalized lactic acid macromonomers via polycondensation as an alternative to ring opening polymerization

Engineered polylactic acid (PLA) nanoparticles synthesized from oligo(lactic acid) macromonomers have been studied over the last decades for controlled drug delivery. These macromonomers are typically produced via ring-opening polymerization (ROP) of the cyclic dimer lactide, initiated by 2-hydroxyethyl methacrylate (HEMA). This reaction route, despite leading to well-defined macromonomers, relies on the production of lactide from lactic acid, which burdens the ROP overall cost for more than 30%. In this work, we report the synthesis of PLA-based macromonomers by direct polycondensation of lactic acid in the presence of HEMA as a valuable alternative to ROP. In particular, we compare the two processes side by side, focusing on the production of three HEMA-LA_n macromonomers, with n = 2, 4, and 6. Detailed kinetic models are developed for both reaction systems, and the corresponding parameters are estimated by fitting the experimental data. Through these models, the reaction kinetics as well as the time evolution of the entire chain length distributions of the products from polycondensation and ROP could be reliably predicted. This way, we demonstrated that polycondensation is a valuable alternative to ROP only for macromonomers with an average chain length of up to 4 and that ROP remains the main route to longer chains, when a strict control over the chain length distribution is required.