Thermal,mechanical, and barrier properties of polyethylene terephthalate‐platelet nanocomposites prepared by in situ polymerization

This study used in situ polymerization to prepare polyethylene terephthalate (PET) nanocomposites incorporating Ethoquad‐modified montmorillonite (eMMT), unmodified hectorite (HCT), or phenyl hectorite (phHCT) particles to study the impact of platelet surface chemistry and loading on thermal, mechanical, and gas barrier properties. eMMT platelets reduced the PET crystallization rate without altering the ultimate degree of crystallinity. In contrast, HCT and phHCT platelets accelerated the polymer's crystallization rate and increased its crystallinity. DMA results for thermally‐quenched samples showed that as T increased past glass transition temperature (T_g), HCT and phHCT nanocomposites (and control PET) manifested precipitous drops in G′ followed by increasing G′ due to cold crystallization; in contrast, eMMT nanocomposites had much higher G′ values around T_g. This provides direct evidence of eMMT reinforcement in thermally‐quenched eMMT nanocomposites. These results suggest that eMMT has a strong, favorable interaction with PET, possibly through Ethoquad‐PET entanglement. HCT and phHCT have a fundamentally different interaction with PET that increases crystallization rate and T_g by 11 to 17°C. Water barrier improvement in eMMT nanocomposites agrees with previously published oxygen barrier results and can be rationalized in terms of a tortuous path gas barrier model. POLYM. ENG. SCI., 52:1888–1902, 2012. © 2012 Society of Plastics Engineers     

Matrix models of discretely bending, stiff polymers

Polymer models which make use of the Ising model and transfer matrix techniques remind us, for example, of the work of Flory [Statistical mechanics of chain molecules, 1969] and Zimm and Bragg [J Chem Phys, 31 (1959) 526]. We investigate the properties of some such polymer models where the chain conformation can be described solely by an Ising-like parameterization and a set of independent, predetermined bond direction vectors or by a Potts-like model for directions of bond vectors on a lattice, with the specific aim of understanding more closely the connection of constraints and forces on the chain ends for polymers which, in general, are of arc length corresponding to their persistence lengths. Instances of these models are directed helical walks, random sequential walks, bimodally distributed in direction walks or relatively short, stiff chains fixed into a network. The behavior of this model under deformation in statistical mechanics and its dynamical properties under Glauber dynamics are discussed.     

Time-dependent viscosity of structured clay suspensions

Time-dependent viscosity of structured clay suspensions under a fixed shear was revealed in the prepared slurry samples of clay lenses from the Athabasca oil sands deposit, differing from thixotropic or rheopectic suspensions. At a lower salt (Na or Ca) concentration, the viscosity oscillated with time, which was slowly damped with increasing salt concentrations. The viscosity increased without reaching a maximum plateau, even after a run of a few hours. At 1000 ppm Na concentration, a maximum viscosity was reached, followed by viscosity fluctuation within a narrow range to approach an equilibrium value with time. Both sample ageing and shear history affected the slurry viscosity. It was speculated that the Brownian motion of colloidal clay particles and the applied shear induced rearrangement and continued formation of clay microstructures with time, due to the rotation of anisotropic colloidal clay particles under simple shear flow. Its implications to oil sands research and operation were briefly discussed.     

5-Ethynyluridine: A Bio-orthogonal Uridine Variant for mRNA-Based Therapies and Vaccines

The identification of pseudo- and N¹-methylpseudo-uridine (Ψ and mΨ, respectively) as immunosilent uridine analogues has propelled the development of mRNA-based vaccines and therapeutics. Here, we have characterised another uridine analogue, 5-ethynyluridine (EU), which has an ethynyl moiety. We show that this uridine analogue does not cause immune activation in human macrophages, as it does not induce interleukin-6 secretion or expression of the inflammatory and antiviral genes MX1, PKR, and TAP2. Moreover, EU allows for prolonged expression, as shown with mRNA coding for yellow fluorescent protein (YFP). Side-by-side comparisons of EU with unmodified, Ψ, and mΨ revealed that EU-modified mRNA is expressed at lower levels, but confers similar stability and low immunogenicity to the other uridine analogues. Furthermore, structure analysis of modified mRNAs suggests that the observed phenotype is largely independent of RNA folding. Thus, EU is a potential candidate for RNA-based vaccines and therapeutics.     

MicroRNA 148a Suppresses Tuberculous Fibrosis by Targeting NOX4 and POLDIP2

Extracellular matrix production by pleural mesothelial cells in response to Mycobacterium tuberculosis contributes to tuberculous fibrosis. NOX4 is involved in the pathogenesis of tuberculous fibrosis. In this study, we evaluated whether NOX4 gene-targeting microRNAs showed protective effects in tuberculosis fibrosis. TargetScan prediction software was used to identify candidate microRNAs that bind the 3′ UTRs of NOX4, and microRNA-148a (miR-148a) was selected as the best miRNA candidate. A repressed and forced expression assay in Met5A cells was performed to investigate the causal relationship between miR-148a and NOX4. The role of miR-148a in tuberculous pleural fibrosis was studied using a murine model of Mycobacterium bovis bacillus Calmette–Guérin (BCG) pleural infection. Heat-killed M. tuberculosis (HKMT) induces NOX4 and POLDIP2 expression. We demonstrated the inhibitory effect of miR-148a on NOX4 and POLDIP2 expression. The increased expression of miR-148a suppressed HKMT-induced collagen-1A synthesis in PMC cells. In the BCG pleurisy model, miR-148a significantly reduced fibrogenesis and epithelial mesenchymal transition. High levels of miR-148a in tuberculous pleural effusion can be interpreted as a self-limiting homeostatic response. Our data indicate that miR-148a may protect against tuberculous pleural fibrosis by regulating NOX4 and POLDIP2.     

ApoA1 Deficiency Reshapes the Phenotypic and Molecular Characteristics of Bone Marrow Adipocytes in Mice

In the present study, we studied the effect of apolipoprotein A-1 (APOA1) on the spatial and molecular characteristics of bone marrow adipocytes, using well-characterized ApoA1 knockout mice. APOA1 is a central regulator of high-density lipoprotein cholesterol (HDL-C) metabolism, and thus HDL; our recent work showed that deficiency of APOA1 increases bone marrow adiposity in mice. We found that ApoA1 deficient mice have greatly elevated adipocytes within their bone marrow compared to wild type counterparts. Morphologically, the increased adipocytes were similar to white adipocytes, and displayed proximal tibial-end localization. Marrow adipocytes from wild type mice were significantly fewer and did not display a bone-end distribution pattern. The mRNA levels of the brown/beige adipocyte-specific markers Ucp1, Dio2, Pat2, and Pgc1a; and the expression of leptin were greatly reduced in the ApoA1 knock-out in comparison to the wild-type mice. In the knock-out mice, adiponectin was remarkably elevated. In keeping with the close ties of hematopoietic stem cells and marrow adipocytes, using flow cytometry we found that the elevated adiposity in the ApoA1 knockout mice is associated with a significant reduction in the compartments of hematopoietic stem cells and common myeloid, but not of the common lymphoid, progenitors. Moreover, the ‘beiging’-related marker osteopontin and the angiogenic factor VEGF were also reduced in the ApoA1 knock-out mice, further supporting the notion that APOA1—and most probably HDL-C—regulate bone marrow microenvironment, favoring beige/brown adipocyte characteristics.     

Sensitiveness of Porous Silicon‐Based Nano‐Energetic Films

Nanoporous silicon (pSi) films on a silicon wafer were loaded with sodium perchlorate and perfluoropolyether (PFPE) oxidizing agents. Sensitiveness to impact, friction and electrostatic discharge (ESD) of the resulting energetic thin films were investigated. It was observed that pSi loaded with perchlorate was sensitive at the lowest limit of detection for the available equipment (<4.9 J impact energy, <5 N friction force, and <45 mJ ESD spark energy). When loaded with PFPE the material was very sensitive to impact (<4.9 J), moderately sensitive to ESD (between 45 and 100 mJ) and insensitive to friction (>360 N). pSi loaded with either perchlorate or PFPE displayed behavior during sensitiveness testing similar to other primary explosive materials.