Vapor barrier properties of polycaprolactone montmorillonite nanocomposites: effect of clay dispersion

Different compositions of poly(ε-caprolactone) (PCL) and (organo-modified) montmorillonite were prepared by melt blending or catalyzed ring opening polymerization of ε-caprolactone. Microphase composites were obtained by direct melt blending of PCL and sodium montmorillonite (MMT-Na⁺). Exfoliated nanocomposites were obtained by in situ ring opening polymerization of ε-caprolactone with an organo-modified montmorillonite (MMT-(OH)₂) by using dibutyltin dimethoxide as an initiator/catalyst. Intercalated nanocomposites were formed either by melt blending with organo-modified montmorillonite or in situ polymerization within sodium montmorillonite. The barrier properties were studied for water vapor and dichloromethane as an organic solvent. The sorption (S) and the zero concentration diffusion coefficient (D₀) were evaluated for both vapors. The water sorption increases with increasing the MMT content, particularly for the microcomposites containing the unmodified MMT-Na⁺. The thermodynamic diffusion parameters, D₀, were compared to the value of the parent PCL: both microcomposites and intercalated nanocomposites show diffusion parameters very near to PCL. At variance exfoliated nanocomposites show much lower values, even for small montmorillonite content. In the case of the organic vapor, the value of sorption at low relative pressure is mainly dominated by the amorphous fraction present in the samples, not showing any preferential adsorption on the inorganic component. At high relative pressure the isotherms showed an exponential increase of sorption, due to plasticization of the polyester matrix. The D₀ parameters were also compared to those of the unfilled PCL; in this case, both the exfoliated and the intercalated samples showed lower values, due to a more tortuous path for the penetrant molecules.     

Depletion kinetics of perfluoropolyether films with functional end groups using molecular dynamics simulation

Molecular dynamics simulation coupled with a coarse-grained model is employed to investigate the surface depletion kinetics of functional polyether film under heat treatment. The real-time evolutions of lubricant film desorption and decomposition are examined during rapid heating and isothermal stages. The reaction order of lubricant depletion is evaluated during the rapid heating using a constant heating rate and various coverages. It reveals that a peak in the desorption (decomposition) rate is formed and is independent of the mass (bond) coverage, which gives rise to a first-order, coverage independent depletion kinetics. The rate constants for lubricant desorption and decomposition are thus calculated based on a first-order kinetics-controlled reaction during the isothermal stage. The kinetics of functional lubricant depletion shows that desorption is the main mechanism of lubricant depletion under rapid and isothermal heat treatment and is the major cause of lubricant thermal instability on the surface.     

Organometallic Pt(II) containing polymer as silver protection against sulfide tarnishing

In this work, the use of a film of an organometallic polymer, namely Pt‐DEBP, has been tested for the selective capture of sulfides with the aim of protecting silver object. Ag foils were exposed to different environmental conditions in the presence of Pt‐DEBP films. Scanning electron microscopy, energy dispersive spectrometry, and colorimetric studies allowed to assess that the polymeric layer selectively captures H₂S, preventing the tarnishing of the silver substrate over a period at least of 2 months, without any manipulation of the sample. This approach open new perspectives for the prevention of aging effects on silver objects of artistic interest, for which cleaning or coating procedures should be avoid. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

RO membrane solute rejection behavior at the initial stage ofcolloidal fouling

This study investigated the rejection of salt and inert organic compounds by reverse osmosis membranes during the initial stage of colloidal fouling. Results of laboratory-scale experiments showed that colloidal fouling caused a marked decrease in flux, salt rejection and rejection of organics with molecular weight (MW) smaller than about 100 g/mol. Removal of neutrally charged organics was mainly by size or steric exclusion. Rejection of xylose, which has MW >100 g/mol, was not affected much by colloidal fouling. The decrease in salt and low MW organic rejections during the initial stage of colloidal fouling was attributed to cake-enhanced concentration polarization, whereby the colloidal cake layer hindered back diffusion of solutes from the membrane surface to the bulk solution, resulting in higher solute concentration gradient across the membrane. At higher channel wall shear rate, the rates of colloidal deposition, flux decline, decrease in salt rejection, and decrease in low MW organic rejection were lower.     

A Cumulative Effect of Food and Viruses to Trigger Celiac Disease (CD): A Commentary on the Recent Literature

Celiac disease (CD) is a type of inflammatory chronic disease caused by nutrients such as gliadin that induce a TC (T cell)-mediated response in a partially known genetical background in an environment predisposed to inflammation, including viruses and food. Various experimental and clinical observations suggest that multiple agents such as viruses and bacteria have some common, inflammatory pathways predisposing individuals to chronic inflammatory diseases including celiac disease (CD). More recently, a Western diet and lifestyle have been linked to tissue inflammation and increase in chronic inflammatory diseases. In CD, the gliadin protein itself has been shown to be able to induce inflammation. A cooperation between viruses and gliadin is present in vitro and in vivo with common mechanisms to induce inflammation. Nutrients could have also a protective effect on CD, and in fact the anti-inflammatory Mediterranean diet has a protective effect on the development of CD in children. The possible impact of these observations on clinical practice is discussed.     

A Phenylacetamide Resveratrol Derivative Exerts Inhibitory Effects on Breast Cancer Cell Growth

Resveratrol (RSV) is a natural compound that displays several pharmacological properties, including anti-cancer actions. However, its clinical application is limited because of its low solubility and bioavailability. Here, the antiproliferative and anti-inflammatory activity of a series of phenylacetamide RSV derivatives has been evaluated in several cancer cell lines. These derivatives contain a monosubstituted aromatic ring that could mimic the RSV phenolic nucleus and a longer flexible chain that could confer a better stability and bioavailability than RSV. Using MTT assay, we demonstrated that most derivatives exerted antiproliferative effects in almost all of the cancer cell lines tested. Among them, derivative 2, that showed greater bioavailability than RSV, was the most active, particularly against estrogen receptor positive (ER+) MCF7 and estrogen receptor negative (ER-) MDA-MB231 breast cancer cell lines. Moreover, we demonstrated that these derivatives, particularly derivative 2, were able to inhibit NO and ROS synthesis and PGE2 secretion in lipopolysaccharide (LPS)-activated U937 human monocytic cells (derived from a histiocytoma). In order to define the molecular mechanisms underlying the antiproliferative effects of derivative 2, we found that it determined cell cycle arrest at the G1 phase, modified the expression of cell cycle regulatory proteins, and ultimately triggered apoptotic cell death in both breast cancer cell lines. Taken together, these results highlight the studied RSV derivatives, particularly derivative 2, as promising tools for the development of new and more bioavailable derivatives useful in the treatment of breast cancer.     

Proprotein Convertase Subtilisin Kexin Type 9 Inhibitors Reduce Platelet Activation Modulating ox-LDL Pathways

Background: Proprotein convertase subtilisin kexin type 9 inhibitors (PCSK9i) lower LDL-cholesterol and slow atherosclerosis preventing cardiovascular events. While it is known that circulating PCSK9 enhances platelet activation (PA) and that PCSK9i reduce it, the underlying mechanism is not still clarified. Methods: In a multicenter before–after study in 80 heterozygous familial hypercholesterolemia (HeFH) patients on treatment with maximum tolerated statin dose ± ezetimibe, PA, soluble-NOX2-derived peptide (sNOX2-dp), and oxidized-LDL (ox-LDL) were measured before and after six months of PCSK9i treatment. In vitro study investigates the effects of plasma from HeFH patients before and after PCK9i on PA in washed platelets (wPLTs) from healthy subjects. Results: Compared to baseline, PCSK9i reduced the serum levels of LDL-c, ox-LDL, Thromboxane (Tx) B2, sNOX2-dp, and PCSK9 (p < 0.001). The decrease of TxB2 correlates with that of ox-LDL, while ox-LDL reduction correlated with PCSK9 and sNOX2-dp delta. In vitro study demonstrated that wPLTs resuspended in plasma from HeFH after PCSK9i treatment induced lower PA and sNOX2-dp release than those obtained using plasma before PCSK9i treatment. This reduction was vanished by adding ox-LDL. ox-LDL-induced PA was blunted by CD36, LOX1, and NOX2 inhibition. Conclusions: PCSK9i treatment reduces PA modulating NOX2 activity and in turn ox-LDL formation in HeFH patients.     

Inherited Retinal Diseases Due to RPE65 Variants: From Genetic Diagnostic Management to Therapy

Inherited retinal diseases (IRDs) are a heterogeneous group of conditions that include retinitis pigmentosa (RP) and Leber congenital amaurosis (LCA) and early-onset severe retinal dystrophy (EO[S]RD), which differ in severity and age of onset. IRDs are caused by mutations in >250 genes. Variants in the RPE65 gene account for 0.6–6% of RP and 3–16% of LCA/EORD cases. Voretigene neparvovec is a gene therapy approved for the treatment of patients with an autosomal recessive retinal dystrophy due to confirmed biallelic RPE65 variants (RPE65-IRDs). Therefore, the accurate molecular diagnosis of RPE65-IRDs is crucial to identify ‘actionable’ genotypes—i.e., genotypes that may benefit from the treatment—and is an integral part of patient management. To date, hundreds of RPE65 variants have been identified, some of which are classified as pathogenic or likely pathogenic, while the significance of others is yet to be established. In this review, we provide an overview of the genetic diagnostic workup needed to select patients that could be eligible for voretigene neparvovec treatment. Careful clinical characterization of patients by multidisciplinary teams of experts, combined with the availability of next-generation sequencing approaches, can accelerate patients’ access to available therapeutic options.     

Cold Spray Deposition of Freestanding Inconel Samples and Comparative Analysis with Selective Laser Melting

Cold spray offers the possibility of obtaining almost zero-porosity buildups with no theoretical limit to the thickness. Moreover, cold spray can eliminate particle melting, evaporation, crystallization, grain growth, unwanted oxidation, undesirable phases and thermally induced tensile residual stresses. Such characteristics can boost its potential to be used as an additive manufacturing technique. Indeed, deposition via cold spray is recently finding its path toward fabrication of freeform components since it can address the common challenges of powder-bed additive manufacturing techniques including major size constraints, deposition rate limitations and high process temperature. Herein, we prepared nickel-based superalloy Inconel 718 samples with cold spray technique and compared them with similar samples fabricated by selective laser melting method. The samples fabricated using both methods were characterized in terms of mechanical strength, microstructural and porosity characteristics, Vickers microhardness and residual stresses distribution. Different heat treatment cycles were applied to the cold-sprayed samples in order to enhance their mechanical characteristics. The obtained data confirm that cold spray technique can be used as a complementary additive manufacturing method for fabrication of high-quality freestanding components where higher deposition rate, larger final size and lower fabrication temperatures are desired.     

Structural modifications induced by recycling of polypropylene

The effect of numerous reprocessing cycles on transport properties of isotactic polypropylene (iPP) films was studied and related to the change of molecular weight and molecular weight distribution occurring during the recycling. Sorption curves of dichloromethane vapor in different samples of iPP were analyzed at 25°C to investigate the effect of structure modifications on the sorption mode. Moreover, gas permeability measurements were performed to evaluate the influence of reprocessing on the gas transport properties. The results obtained were attributed to modifications in the molecular structure of the polymer, evidenced from gel permeation chromatography (GPC), and to a different morphology of the films, as results from X-ray diffractograms and dynamic-mechanical thermal analysis (DMTA).