Activated carbon and metal organic framework as adsorbent for low-pressure methane storage applications: an overview

The aim of this comprehensive review on materials for methane storage application is to understand which are the best conditions and the best materials for their use for the implementation of storage tank. The research was focused on two different families of samples that up to now appear like the most promising. In particular, Activated carbon and metal organic framework were analyzed and an overall picture was extrapolated. Analysis of the structural parameters and adsorption capacities were evaluated and relation between them were obtained. A comparison of values available in literature was done and, when possible, laboratory tests were performed. The presented results allow to identify potential materials with high specific storage capacity and to verify their performances in optimized conditions. This work represents the starting point for a real and efficient method to the methane storage as a starting point for the development of Adsorbed Natural Gas technology for static and/or automotive applications.     

Polymer layered silicate nanocomposites

Polymers filled with low amounts of layered silicate dispersed at nanoscale level are most promising materials characterized by a combination of chemical, physical and mechanical properties that cannot be obtained with macro‐ or microscopic dispersions of inorganic fillers. Polymer layered silicate nanocomposites can be obtained by insertion of polymer molecules in the galleries between the layers of phyllosilicate. Here, hydrated alkaline or alkaline earth metal cations are hosted which neutralize the negative charge resulting from isomorphous substitutions of Mg or Al cations within the silicate. Insertion of polymer molecules to prepare “intercalation hybrids” can be carried out by replacing the water hydration molecules in the galleries by polymers containing polar functional groups, using the so called ion‐dipole method. A more general technique involves compatibilization of the silicate by intercalation of an organic molecule, typically an organic alkylammonium salt, that replaces the cations in the interlayer galleries to form an organically modified layered silicate (OLS). The aliphatic chain of the OLS favors the intercalation of any type of polymer. Intercalated or delaminated polymer‐silicate hybrids are obtained depending on whether the stack organization of the silicate layers is preserved or is lost, with single sheets being distributed in the polymer matrix. The methods currently used for preparing polymer layered silicate (PLS) nanocomposites are: in situ polymerization, from polymer solution, or from polymer melt. Although PLS nanocomposites have been known for a long time, it is the possibility of preparing them by melt intercalation of OLS in processing that is boosting the present interest in these materials and their properties. So far PLS nanocomposites have been characterized by X‐ray diffractometry, transmission electron microscopy, differential scanning calorimetry, and NMR. Published results on PLS nanocomposites are reviewed concerning their characterization and properties with particular reference to fire retardant behavior.     

Fluoroelastomers-dependence of relaxation phenomena on composition

The dynamic-mechanical properties of some fluoroelastomers were determined as a function of composition at low frequency (≈ 1 Hz), by means of a free oscillation torsion pendulum, between −180°C and the softening point. Vinylidenefluoride (VDF)-hexafluoropropene (HFP) copolymers of molar composition 0–39% HFP and terpolymers of VDF and HFP with up to 30mol% tetrafluoroethylene (TFE) and a constant VDF to HFP molar ratio of 3.4 were considered. Two relaxation processes typical of the amorphous phase were found. The first, located at about −87°C, is related to local motions and the transition temperature was found to be independent of composition for copolymers, while it depends on TFE molar content for terpolymers. The second is related to the glass transition and the transition temperature depends on the composition. However, for semicrystalline copolymers the double glass transition phenomenon was observed. When crystallinity goes to zero at about 20 mol% HFP, only one transition is observed. It was also found that ordered structures can take place for terpolymers when TFE molar concentration exceeds 20%. The crystal disorder transition of pure PVDF (75°C) is observed also for low HFP concentrations but the transition temperature is strongly reduced. Analogies between the VDF-HFP and E-P systems are also discussed.     

Structure-activity relationship study of 16 a-thiocamptothecins: an integrated in vitro and in silico approach

The instability of the hydroxylactone E ring represents a critical drawback of camptothecins, because the lactone ring is recognized to be essential for stabilization of topoisomerase I‐mediated DNA cleavage. In an attempt to investigate the effect of the thiopyridone pharmacophofore on the molecular and pharmacological features of the drug, we prepared a series of novel 16 a‐thiocamptothecin analogues. Due to the sulfur atom, a destabilization of the hydrogen bond between the hydroxy group in position 17 of the opened E ring and the carbonyl of the pyridone moiety is predicted, thus shifting the equilibrium toward the closed lactone form and increasing the lipophilic properties of the compounds. This feature was associated with superior antiproliferative potency, with reduced interaction with the human serum albumin and with substantial increase of the persistence of the topoisomerase I–DNA cleavable complex. These effects were prominent for thio‐SN38, the most active compound of the series. The favorable interactions at the molecular and cellular level of the reported thiocamptothecins confer promising features, and these compounds warrant preclinical development.     

Structure and thermal properties of heat treated plasma sprayed ceria–yttria co-stabilized zirconia coatings

Thick plasma sprayed thermal barrier coatings are suitable for thermal and hot corrosion protection of metal components in land-based turbine and diesel engines. In this work, ceria–yttria co-stabilized zirconia coatings were deposited by atmospheric plasma spraying in a mixture of non-transformable tetragonal t′ and cubic c zirconia phases. Free-standing coatings were isothermally annealed at 1315 °C for different times and their crystal structure was studied by XRD. No phase decomposition occurred. Columnar grains grew in the molten splats with increasing annealing time according to a preferential direction and, after 50 h of heat treatment, they were partially replaced by equiaxed grains. Both in-plane and out-of-plane thermal expansion coefficients (CTEs) were measured from coating expansion during heating. The CTE was slightly sensitive to thermal exposure in out-of-plane direction, whereas it kept almost constant in plane direction. The specific heat capacity Cp of annealed coatings, measured by differential scanning calorimetry (DSC), decreased in comparison with as-sprayed coating, due to high-temperature sintering.     

Identification of Rare LRP5 Variants in a Cohort of Males with Impaired Bone Mass

Osteoporosis is the most common bone disease characterized by reduced bone mass and increased bone fragility. Genetic contribution is one of the main causes of primary osteoporosis; therefore, both genders are affected by this skeletal disorder. Nonetheless, osteoporosis in men has received little attention, thus being underestimated and undertreated. The aim of this study was to identify novel genetic variants in a cohort of 128 males with idiopathic low bone mass using a next-generation sequencing (NGS) panel including genes whose mutations could result in reduced bone mineral density (BMD). Genetic analysis detected in eleven patients ten rare heterozygous variants within the LRP5 gene, which were categorized as VUS (variant of uncertain significance), likely pathogenic and benign variants according to American College of Medical Genetics and Genomics (ACMG) guidelines. Protein structural and Bayesian analysis performed on identified LRP5 variants pointed out p.R1036Q and p.R1135C as pathogenic, therefore suggesting the likely association of these two variants with the low bone mass phenotype. In conclusion, this study expands our understanding on the importance of a functional LRP5 protein in bone formation and highlights the necessity to sequence this gene in subjects with idiopathic low BMD.     

Fertility-Sparing Approach in Women Affected by Stage I and Low-Grade Endometrial Carcinoma: An Updated Overview

Endometrial cancer (EC) is a deleterious condition which strongly affects a woman’s quality of life. Although aggressive interventions should be considered to treat high-grade EC, a conservative approach should be taken into consideration for women wishing to conceive. In this scenario, we present an overview about the EC fertility-sparing approach state of art. Type I EC at low stage is the only histological type which can be addressed with a fertility-sparing approach. Moreover, no myometrium and/or adnexal invasion should be seen, and lymph-vascular space should not be involved. Regarding the pharmaceutical target, progestins, in particular medroxyprogesterone acetate (MPA) or megestrol acetate (MA), are the most employed agent in conservative treatment of early-stage EC. The metformin usage and hysteroscopic assessment is still under debate, despite promising results. Particularly strict and imperious attention should be given to the follow-up and psychological wellbeing of women, especially because of the double detrimental impairment: both EC and EC-related infertility consequences.     

Direct and Indirect Effect of TGFβ on Treg Transendothelial Recruitment in HCC Tissue Microenvironment

The balance between anti-tumor and tumor-promoting immune cells, such as CD4+ Th1 and regulatory T cells (Tregs), respectively, is assumed to dictate the progression of hepatocellular carcinoma (HCC). The transforming growth factor beta (TGFβ) markedly shapes the HCC microenvironment, regulating the activation state of multiple leukocyte subsets and driving the differentiation of cancer associated fibroblasts (CAFs). The fibrotic (desmoplastic) reaction in HCC tissue strongly depends on CAFs activity. In this study, we attempted to assess the role of TGFβ on transendothelial migration of Th1-oriented and Treg-oriented CD4+ T cells via a direct or indirect, CAF-mediated mechanisms, respectively. We found that the blockage of TGFβ receptor I-dependent signaling in Tregs resulted in impaired transendothelial migration (TEM) of these cells. Interestingly, the secretome of TGFβ-treated CAFs inhibited the TEM of Tregs but not Th1 cells, in comparison to the secretome of untreated CAFs. In addition, we found a significant inverse correlation between alpha-SMA and FoxP3 (marker of Tregs) mRNA expression in a microarray analysis involving 78 HCCs, thus suggesting that TGFβ-activated stromal cells may counteract the trafficking of Tregs into the tumor. The apparent dual behavior of TGFβ as both pro- and anti-tumorigenic cytokines may add a further level of complexity to the mechanisms that regulate the interactions among cancerous, stromal, and immune cells within HCC, as well as other solid tumors, and contribute to better manipulation of the TGFβ signaling as a therapeutic target in HCC patients.     

Gold(I) and gold(III) complexes with anionic oxygen donor ligands: hydroxo, oxo and alkoxo complexes

The chemistry of gold(I) and gold(III) hydroxo, oxo and alkoxo complexes containing organic co-ligands is reviewed. Due to the high reactivity of the gold-oxygen bond most of these species can be employed as useful intermediates in many important processes. Alkoxides are by far the most numerous class among these species, and both gold(I) and gold(III) complexes are known with a variety of alkoxides. The recent discovery of the catalytic activity of some gold(I) and gold(III) fluoroalkoxides has enlivened the interest towards this class of compounds leading to new applications for previously known complexes, as is the case for a gold(III) siloxo complex which has found use as a precursor for CVD, as well as for the synthesis of new alkoxo derivatives. Another well represented and well known class of compounds are the gold(I) oxo complexes [O(AuPR₃)₃]⁺ which are the most effective aurating reagents. Gold(III) oxo complexes have been synthesized only recently and much of their chemistry is still largely to be explored. Preliminary studies suggest their potential in the transfer of oxygen atoms. Finally, some cationic gold(III) hydroxo complexes are found to display significant,and in some cases relevant, cytotoxic effects on cancer cell lines.