Melting behavior,crystallization kinetics and morphology of random copolyesters of poly(2‐hydroxyethoxybenzoate) with ε‐caprolactone

The melting behavior after isothermal crystallization and the crystallization kinetics of random poly(2‐hydroxyethoxybenzoate/ε‐caprolactone) copolymers rich in 2hydroxyethoxybenzoate units were investigated by means of differential scanning calorimetry and hot‐stage optical microscopy. The observed multiple endotherms, which are commonly displayed by polyesters, were found to be influenced both by crystallization temperature and composition. By applying the Hoffman‐Weeks method to the melting temperatures of isothermally crystallized samples, the equilibrium melting temperatures of the copolymers were obtained. Furthermore, isothemal crystallization kinetics was analyzed according to the Avrami treatment. Values of the exponent n close to 3 were obtained, independently of crystallization temperature and composition, in agreement with a crystallization process originating from predeterminated nuclei and characterized by three‐dimensional spherulitic growth. Space‐filling banded spherulites were observed by hot‐stage optical polarizing microscopy at all the crystallization temperatures explored, the band spacing being affected by both crystallization temperature and composition. As expected, the introduction of ε‐caprolactone comonomeric units in the polymer chain of PHEBA was found to decrease its crystallization rate.     

Asymmetric Dimethylarginine Plasma Levels and Endothelial Function in Newly Diagnosed Type 2 Diabetic Patients

It is now well established that major risk factors for cardiovascular diseases (CVD) impact upon endothelial function by decreasing nitric oxide (NO) bioavailability. Asymmetric dimethylarginine (ADMA), an endogenous analog of l-arginine, is able to inhibit the activity of endothelial-NO synthase, promoting endothelial dysfunction. Type 2 diabetes (T2D) is characterized by a reduced endothelium-dependent vasodilation and increased ADMA levels and ADMA is strongly associated with micro- and macrovascular diabetic complications. However, there are not a lot of data about the role of ADMA on endothelial function in newly diagnosed T2D patients without cardiovascular (CV) complications. For this aim, we have enrolled forty-five newly diagnosed T2D patients, evaluated by a oral glucose tolerance test, and thirty normal subjects. Endothelium-dependent and -independent vasodilatation was investigated by intra-arterial infusion of increasing doses of acetylcholine (ACh) and sodium nitroprusside. ADMA was measured by high-performance liquid chromatography and insulin resistance (IR) by HOMA. Newly diagnosed T2D patients showed higher ADMA and l-arginine mean values in comparison with normal subjects and a significantly reduced ACh-stimulated forearm blood flow (FBF). In T2D patients FBF was significantly and inversely correlated with ADMA (r = −0.524, p < 0.0001) and in a multivariate regression analysis, ADMA resulted the stronger predictor of FBF, explaining the 27.5% of variability (p < 0.0001). In conclusion, ADMA was strongly related to endothelial dysfunction also in patients with newly diagnosed T2D, without clinically manifest vascular complications. This field is of great interest for understanding the mechanisms underlying the pathogenesis of diabetic disease and its CV complications.     

Unpatterned Bioactive Poly(Butylene 1,4-Cyclohexanedicarboxylate)-Based Film Fast Induced Neuronal-Like Differentiation of Human Bone Marrow-Mesenchymal Stem Cells

Herein, we present poly(butylene 1,4-cyclohexanedicarboxylate) (PBCE) films characterized by an unpatterned microstructure and a specific hydrophobicity, capable of boosting a drastic cytoskeleton architecture remodeling, culminating with the neuronal-like differentiation of human bone marrow-mesenchymal stem cells (hBM-MSCs). We have used two different filming procedures to prepare the films, solvent casting (PBCE) and compression-moulding (PBCE*). PBCE film had a rough and porous surface with spherulite-like aggregations (Ø = 10–20 μm) and was characterized by a water contact angle = 100°. PBCE* showed a smooth and continuous surface without voids and visible spherulite-like aggregations and was more hydrophobic (WCA = 110°). Both surface characteristics were modulated through the copolymerization of different amounts of ether-oxygen-containing co-units into PBCE chemical structure. We showed that only the surface characteristics of PBCE-solvent-casted films steered hBM-MSCs toward a neuronal-like differentiation. hBM-MSCs lost their canonical mesenchymal morphology, acquired a neuronal polarized shape with a long cell protrusion (≥150 μm), expressed neuron-specific class III β-tubulin and microtubule-associated protein 2 neuronal markers, while nestin, a marker of uncommitted stem cells, was drastically silenced. These events were observed as early as 2-days after cell seeding. Of note, the phenomenon was totally absent on PBCE* film, as hBM-MSCs maintained the mesenchymal shape and behavior and did not express neuronal/glial markers.     

Melting behavior and crystallization kinetics of poly(butylene terephthalate‐co‐diethylene terephthalate) and poly(butylene terephthalate‐co‐triethylene terephthalate) copolyesters

The melting behavior of poly(butylene terephthalate‐co‐diethylene terephthalate) and poly(butylene terephthalate‐co‐triethylene terephthalate) copolymers was investigated by differential scanning calorimetry after isothermal crystallization from the melt. Multiple endotherms were found for all the samples, and attributed to the melting and recrystallization processes. By applying the Hoffman‐Weeks' method, the equilibrium melting temperatures of the copolymers under investigation were obtained. Two distinct peaks in the crystallization exothermic curve were observed for all the samples. Both of them appeared at higher times than that of PBT, indicating that the introduction of a comonomer decreased the crystallization rate. The observed dependence of this latter on composition was explained on the basis of the content of ether–oxygen atoms in diethylene and triethylene terephthalate units, and of the different sizes of these units. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 81: 3545–3551, 2001     

Extraction of polymer stress–strain behavior in the presence of self‐heating by the use of a simple model for the elastic–plastic deformation

Polymer materials are well known to be sensitive to strain rate and temperature. Self‐heating and friction effects also play an important role in the mechanical response of these materials. Numerous constitutive laws and phenomenological models have been developed to take into account these dependencies. This article proposes a simplified phenomenological model based on a mapping technique for the strain rate and temperature dependence. The effects of friction and adiabatic heating are also analyzed in this work. Relatively good results are obtained compared to experimental results for polypropylene and polychlorotrifluoroethylene. A parametric investigation of the effects of the interfacial equivalent stress (between the specimen and the compressive bars) and the fraction of plastic work converted into heat was performed. This parametric study allowed for a good approximation of these two parameters for the two studied polymers. POLYM. ENG. SCI., 55:2474–2481, 2015. © 2015 Society of Plastics Engineers     

Effects of water vapor on the oxidation and the fracture strength of SiC layer in TRISO fuel particles

Steam oxidation of silicon carbide (SiC) layer in nuclear fuel particles were performed in flowing argon‐water vapor mixture with a total pressure of 1 bar at 1173‐1673 K. Both the phase composition and the microstructure of the oxide scale on the SiC layer varied with the oxidation temperature. Reaction rates of water vapor with the SiC layer were determined by measuring the oxide scale thickness. It was found that the oxidation of SiC layer follows the parabolic law. The activation energy was calculated to be 103±11 kJ/mol. It is proposed that the rate determine step of the oxidation is the diffusion of water vapor molecules in the oxide scale. The fracture strength of SiC shell after steam oxidation was evaluated using a crush test. The fracture strength decreased with the increase in the oxidation temperature due to the thinning of the SiC layer.     

Thermally stable antimicrobial polyvinylchloride/maleimido aromatic hydrazide composites

Antimicrobial novel substituted maleimido aromatic hydrazides were synthesized from N‐[4‐(chlorocarbonyl) phenyl] maleimide with salicylhydrazide, p‐aminobenzohydrazide, or p‐aminosalicylhydrazide. They were characterized by Fourier transform infrared (FTIR), hydrogen‐1 nuclear magnetic resonance (¹H‐NMR), mass spectra, elemental analyses, and antimicrobial activities. These derivatives were investigated as thermal stabilizers for rigid poly(vinyl chloride) (PVC) at 180°C in air by measuring the rate of dehydrochlorination, the extent of discoloration, and the changes that occurred in the molecular masses of the degraded PVC samples. The previously reported stabilizing efficiency data of a nonsubstituted derivative, which was synthesized from N‐[4‐(chlorocarbonyl) phenyl] maleimide with benzohydrazide, is also given for comparison. The results reveal the greater stabilizing efficiency of the investigated derivatives as shown by their longer thermal stability (Ts) periods and lower dehydrochlorination rates in relation to dibasic lead carbonate, cadmium‐barium‐zinc stearate, and n‐octyltin mercaptide industrial stabilizers. The stabilizing efficiency increases with the introduction of electron donating substituent groups in the aromatic ring of the stabilizer molecules. Moreover, the investigated stabilizers impart better color stability for the degraded samples as compared with the reference stabilizers. A synergistic effect is achieved when the materials under investigation were mixed in various weight ratios with any of the reference stabilizers, reaching its maximum at equivalent weight ratio of the investigated stabilizer to the reference one. J. VINYL ADDIT. TECHNOL., 22:247–258, 2016. © 2014 Society of Plastics Engineers     

Does carbon nanopowder threaten amphibian development?

Lethal and teratogenic potentials of carbon nanoparticles (CNPs) in their amorphous form were investigated by the standardized Frog Embryo Teratogenesis Assay-Xenopus (FETAX), a 96-h in vitro whole-embryo toxicity test based on the amphibian Xenopus laevis. Embryos were acutely exposed to 1, 10, 100 and 500 mg/L CNP suspensions and evaluated for lethality, malformations and growth inhibition. Larvae were processed for histological and ultrastructural analyses to detect the main affected organs, to look for specific lesions at the subcellular level and to image and track CNPs into tissues. Only the highest CNP suspension resulted in being embryolethal for X. laevis larvae, while malformed larva percentages significantly differed from controls starting from 100 mg/L. The stomach and gut were the preferential CNP accumulation sites, on the contrary, the digestive epithelium remained intact. The analyses showed the presence of isolated nanoparticles and/or aggregates in different secondary target organs. CNPs were found in circulating erythrocytes. The research confirms the good tolerance of X. laevis towards pure elemental carbon in its nanoparticulate amorphous form, but highlights the possibility of CNP transfer toward all body areas.     

Microwave-assisted synthesis of isosorbide-derived diols for the preparation of thermally stable thermoplastic polyurethane

In order to prepare thermally stable isosorbide-derived thermoplastic polyurethane, the synthesis of two new chiral exo–exo configured diols, prepared from isosorbide, and two types of diphenols (bisphenol A and thiodiphenol) was described. The synthesis conditions were optimized under conventional heating and microwave irradiations. To prove their suitability in polymerization, these monomers were successfully polymerized using 4,4′-diphenylmethane diisocyanate (MDI) and hexamethylene diisocyanate (HDI). Both monomers and polymers have been studied by NMR, FT-IR, TGA, DSC; intrinsic viscosity of polymers has also been determined. The results showed the effectiveness of the synthetic strategy proposed; moreover, a dramatic reduction of the reaction time and an important improvement of the monomers yield using microwave irradiation have been demonstrated. The monomers, as well as the polymers, showed excellent thermal stability both in air and nitrogen. It was also shown that the introduction of sulphur in the polyurethane backbone was effective in delaying the onset of degradation as well as the degradation rate.     

Effects of particulate matter on inflammatory markers in the general adult population

Background

Particulate air pollution is associated with increased risk of cardiovascular disease and stroke. Although the precise mechanisms underlying this association are still unclear, the induction of systemic inflammation following particle inhalation represents a plausible mechanistic pathway.

Methods

We used baseline data from the CoLaus Study including 6183 adult participants residing in Lausanne, Switzerland. We analyzed the association of short-term exposure to PM₁₀ (on the day of examination visit) with continuous circulating serum levels of high-sensitive C-reactive protein (hs-CRP), interleukin 1-beta (IL-1??), interleukin 6 (IL-6), and tumor-necrosis-factor alpha (TNF-??) by robust linear regressions, controlling for potential confounding factors and assessing effect modification.

Results

In adjusted analyses, for every 10???g/m³ elevation in PM₁₀, IL-1? increased by 0.034 (95?% confidence interval, 0.007-0.060) pg/mL, IL-6 by 0.036 (0.015-0.057) pg/mL, and TNF-?? by 0.024 (0.013-0.035) pg/mL, whereas no significant association was found with hs-CRP levels.

Conclusions

Short-term exposure to PM₁₀ was positively associated with higher levels of circulating IL-1?, IL-6 and TNF-?? in the adult general population. This positive association suggests a link between air pollution and cardiovascular risk, although further studies are needed to clarify the mechanistic pathway linking PM₁₀ to cardiovascular risk.