A comprehensive investigation of dye–chitosan blended films for green chemistry applications

In this paper, the ability of chitosan film to remove dyestuff from wastewater was evaluated for environmental applications, using three commercial direct azo dyes. Two chitosan films were adopted: the standard one prepared following a well‐known procedure to form it, and a novel one, with a weakly acidic character. Moreover, to improve the adsorption process, the hydrophobic character of the films was investigated. The pH of the dye solutions was also changed, showing an excellent ability in dye removal at pH 12. The films were characterized by means of spectroscopic and morphologic methods to better understand the nature of interactions between dyes and chitosan chains. Swelling ratio measurements were also performed. All analyses suggest that all dyes showed a strong affinity to chitosan polymer chains, with the presence of extended hydrogen bonds and Van der Waals forces perturbing the chitosan network. Interestingly, very good results were obtained in recycling experiments related to the dyeing capacities of chitosan blended films in the presence of textiles. An ecofriendly application is thus presented in this paper. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 45945.     

Opening Doors to Future Electrochemical Energy Devices: The Anion‐Conducting Polyketone Polyelectrolytes

The numerous potential benefits of incorporating anion‐exchange membranes (AEMs), in place of proton‐exchange membranes (PEMs), in energy storage and conversion technologies renders their development of fundamental importance for the continued evolution of alternative energy systems. However, the widespread implementation of AEMs is currently plagued by a range of problems including lower conductivity (with respect to PEMs), poor stability, and high cost. This study reports the conversion of polyketone, one of the world's most mass produced and cheap polymers, to a new highly tuneable polymer architecture, functionalized polyketone (FPK), that demonstrates a range of excellent properties rendering it a significant prospect for AEM materials. The thermal, processing, and ion‐conducting properties of FPK are governed by the amount and nature of the newly formed N‐substituted pyrrole pendant side groups. At 80 °C, the quarternized pyridyl FPK derivative (4MPyrFPK) yields ion‐conductivities of 8.6 and 10.5 mS cm^?1 in the iodide and hydroxide forms. In addition, the hydroxide form of 4MPyr‐FPK demonstrates remarkable stability toward the typically problematic alkaline conditions. No chemical decomposition is observed to the membrane after imbibing it in KOH solution for 72 h, and furthermore, the ion‐conductivity is demonstrated to remain constant for at least 30 d at 80 °C.     

Element shape design of 2-D CMUT arrays for reducing grating lobes

Fully populated two-dimensional (2-D) arrays are needed to produce high quality ultrasonic volumetric images for real-time applications, but they present many challenges for their physical realization because of the large number of elements. In fact, lambda/2 and lambda minimum spacing between elements is required, respectively, for pyramidal and rectilinear scanning in order to avoid unwanted grating lobes (GLs). However, in past years, capacitive micromachined ultrasonic transducer (CMUT) technology has made possible the production of arrays with large flexibility in element shape and size. In this paper, this property is analyzed, and a new element shape, based on the concept of spatial interpenetration of adjacent elements, is proposed in order to design fully populated 2-D CMUT arrays with a low number of elements, whose beam characteristics are valid for volumetric imaging. Through the use of simulations, it is demonstrated that arrays with pitch larger than lambda (up to 3lambda) used for rectilinear scanning, have notably lower GLs than the equivalent standard arrays designed according to the classical squared element shape. As consequence, the proposed geometry has the advantage of reducing the number of elements (up to a factor of 9) and of enlarging the element size, implying an increase of the SNR relative to the single element. When beam steering is required, arrays can be designed with pitch equal to lambda, reducing the number of elements by a factor of 4 if the maximum steering angle is limited to +/-15 degrees .     

Toward a Magnesium‐Iodine Battery

The quest for new electrolyte and cathode materials is a crucial point for beyond‐lithium‐ion energy storage systems. Following this, an electrolyte for secondary magnesium batteries based on a new iodoaluminate ionic liquid and δ‐MgI₂ is reported. Promising electrochemical performance in terms of Mg plating‐stripping, coulombic efficiency, and conductivity, demonstrates the potential of this iodine‐based system for future Mg secondary batteries.     

Determination of the conformation of the human VDAC1 N-terminal peptide, a protein moiety essential for the functional properties of the pore

Mitochondrial porin or VDAC (voltage-dependent anion-selective channel) is the most abundant protein in the mitochondrial outer membrane. The structure of VDAC has been predicted to be a transmembrane beta-barrel with an alpha-helix at the N terminus. It is a matter of debate as to whether this putative alpha-helix plays a structural role as a component of the pore walls or a function in the pore activity. We have synthesised the human VDAC1 (HVDAC1) N-terminal peptide Ac-AVPPTYADLGKSARDVFTK-NH2 (Prn2-20) and determined its structure by CD and NMR spectroscopy. CD studies show that the Prn2-20 peptide exists in aqueous solvent as an unstructured peptide with no stable secondary structure. In membrane-mimetic SDS micelles or water/trifluoroethanol, however, it assumes an amphipathic alpha-helix conformation between Tyr5 and Val16, as deduced from NMR. No ordered structure was observed in dodecyl beta-maltoside. Differential scanning calorimetric measurements were carried out in order to examine the membrane affinity of the peptide. Upon interaction with the negatively charged 1,2 dipalmitoyl-sn-glycero-3-phosphoserine membrane, Prn2-20 exhibited distinctive behaviour, suggesting that electrostatics play an important role. Interaction between the peptide and artificial bilayers indicates that the peptide lies on the membrane surface. Recombinant HVDAC1 deletion mutants, devoid of seven or 19 N-terminal amino acids, were used for transfection of eukaryotic cells. Over-expression of HVDAC1 increases the number of Cos cells with depolarised mitochondria, and this effect is progressively reduced in cells transfected with HVDAC1 lacking those seven or 19 amino acids. The mitochondrial targeting of the deletion mutants is unaffected. The overall picture emerging from our experiments is that the VDAC N-terminal peptide plays a role in the proper function of this protein during apoptotic events.     

Hybrid inorganic-organic proton conducting membranes based on Nafion and 5 wt.% of MxOy (M = Ti, Zr, Hf, Ta and W): Part I. Synthesis, properties and vibrational studies

This paper describes the effect of nanopowders acting as fillers on the structure and properties of [Nafion/(M_xO_y)_n] membranes with n = 5 wt.%. The films were prepared by a solvent casting procedure using M_xO_y oxoclusters (M = Ti, Zr, Hf, Ta and W) and Nafion. Five new homogeneous membranes were prepared with thicknesses ranging from 170 to 350 μm. The membranes were characterized by means of thermal analyses carried out by thermogravimetry (TG), morphological measurements by scanning electron microscopy (ESEM) and vibrational spectroscopy by FT-IR ATR, FT-Raman measurements. Vibrational investigations allowed us to obtain information on: (a) the network structure and the conformation of fluorocarbon hydrophobic domains of the Nafion host polymer, (b) the M_xO_y?HSO₃R interactions occurring in ionic polar cages of membranes and (c) the various water domains present in the hydrophilic polar cages of membranes. TG allowed us to determine that the membranes are thermally stable up to about 170 °C.In conclusion, it was disclosed that: (a) the hydrophobic Nafion polymer host domains consist of a blend of PTFE chains with helical conformations 10₃ and 15₇ and (b) the fraction of each fluorocarbon helical conformation is modulated by the type of nano-fillers and the dynamic cross-links RSO₃H?M_xO_y?HSO₃R which occur in hydrophilic polar cages of membranes. In hydrophobic domains of Nafion, the highest percentage of fluorocarbon chains with helical conformation 10₃ is observed for [Nafion/(HfO₂)_n] composite membrane, ρ (%) = 16.     

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.     

Insights into Intra-Tumoral Heterogeneity: Transcriptional Profiling of Chemoresistant MPM Cell Subpopulations Reveals Involvement of NFkB and DNA Repair Pathways and Contributes a Prognostic Signature

Chemoresistance is a hallmark of malignant pleural mesothelioma (MPM) management and the expression of ALDH1A3 is responsible for the survival and activity of MPM chemoresistant cell subpopulations (ALDH^bright cells). We enriched mesothelioma ALDH^bright cells to near homogeneity by FACS sorting and an Aldefluor assay and performed unbiased Affymetrix gene expression profiling. Viability and ELISA assays were used to rule out significant apoptosis in the sorted cell subpopulations and to assess target engagement by butein. Statistical analysis of the results, pathway enrichment and promoter enrichment were employed for the generation of the data. Q-RTPCR was used to validate a subset of the identified, modulated mRNAs In this work, we started from the observation that the mRNA levels of the ALDH1A3 isoform could prognostically stratify MPM patients. Thus, we purified MPM ALDH^bright cells from NCI-H2595 cells and interrogated their gene expression (GES) profile. We analyzed the GES of the purified cells at both a steady state and upon treatment with butein (a multifunctional tetrahydroxy-chalcone), which abates the ALDH^bright cell number, thereby exerting chemo-sensitizing effects in vitro and in vivo. We identified 924 genes modulated in a statistically significant manner as a function of ALDH status and of the response to the inhibitor. Pathway and promoter enrichment identified the molecular determinant of high ALDH status and how butein treatment altered the molecular portrait of those chemoresistant cell subpopulations. Further, we unraveled an eighteen-gene signature with high prognostic significance for MPM patients, and showed that most of the identified prognostic contributors escaped the analysis of unfractionated samples. This work proves that digging into the unexplored field of intra-tumor heterogeneity (ITH) by working at the cell subpopulation level may provide findings of prognostic relevance, in addition to mechanistic insights into tumor resistance to therapy.     

Thermal degradation of ethylene–carbon monoxide alternating copolymer under inert atmosphere

This work aims to understand the mechanism of the thermal degradation of the ethylene–carbon monoxide (E-CO) alternating copolymer under mild conditions. The copolymer was subjected to accelerated ageing in an oven at different temperatures below the copolymer melting point, under argon atmosphere, and in the absence of light. The properties of the aged samples were compared with the properties of the untreated copolymer. Untreated and aged samples were analysed by mass spectroscopy (MS) with the direct introduction probe (DIP) and pyrolysis (Py) techniques. The accelerated ageing experiments showed that the thermal degradation of the E-CO alternating copolymer under inert atmosphere is characterized by chain cross-linking, loss of water, and changes in the UV absorption spectrum. The IR spectrum shows modifications only for highly degraded samples in which O−H and C=C groups are present. The experiments performed with the DIP-MS technique have confirmed that the E-CO alternating copolymer loses water during its thermal ageing. The pyrolysis products of the copolymer are linear molecules with 1,4-diketonic structure, 2-cyclopentenone derivatives, alkyl furans, and aromatic compounds. These results suggest that during the thermal degradation of the E-CO alternating copolymer under inert atmosphere, and at low temperatures, aldol condensations and/or dehydration to furan rings probably occur. © 1998 SCI.     

Effect of extraction systems on the phenolic composition of virgin olive oils

The effect of extraction systems on the phenolic composition of virgin olive oils obtained from two different Italian cultivars (Coratina and Oliarola) was determined. The oils extracted using two-phase centrifugation showed in all cases higher phenolic concentration in comparison to oils obtained from three-phase centrifugation. In particular, the highest differences were observed for aglykone derivatives of oleuropein (3,4-DHPEA-EDA and 3,4-DHPEA-EA) that are the most concentrated antioxidant phenolic compounds of virgin olive oil. These results were confirmed by the autoxidation stability of the oils examined.