Nano‐Architectured Composite Anode Enabling Long‐Term Cycling Stability for High‐Capacity Lithium‐Ion Batteries

Failure mechanisms associated with silicon‐based anodes are limiting the implementation of high‐capacity lithium‐ion batteries. Understanding the aging mechanism that deteriorates the anode performance and introducing novel‐architectured composites offer new possibilities for improving the functionality of the electrodes. Here, the characterization of nano‐architectured composite anode composed of active amorphous silicon domains (a‐Si, 20 nm) and crystalline iron disilicide (c‐FeSi₂, 5–15 nm) alloyed particles dispersed in a graphite matrix is reported. This unique hierarchical architecture yields long‐term mechanical, structural, and cycling stability. Using advanced electron microscopy techniques, the nanoscale morphology and chemical evolution of the active particles upon lithiation/delithiation are investigated. Due to the volumetric variations of Si during lithiation/delithiation, the morphology of the a‐Si/c‐FeSi₂ alloy evolves from a core‐shell to a tree‐branch type structure, wherein the continuous network of the active a‐Si remains intact yielding capacity retention of 70% after 700 cycles. The root cause of electrode polarization, initial capacity fading, and electrode swelling is discussed and has profound implications for the development of stable lithium‐ion batteries.     

Chromogenic Photonic Crystal Sensors Enabled by Multistimuli‐Responsive Shape Memory Polymers

Here novel chromogenic photonic crystal sensors based on smart shape memory polymers (SMPs) comprising polyester/polyether‐based urethane acrylates blended with tripropylene glycol diacrylate are reported, which exhibit nontraditional all‐room‐temperature shape memory (SM) effects. Stepwise recovery of the collapsed macropores with 350 nm diameter created by a “cold” programming process leads to easily perceived color changes that can be correlated with the concentrations of swelling analytes in complex, multicomponent nonswelling mixtures. High sensitivity (as low as 10 ppm) and unprecedented measurement range (from 10 ppm to 30 vol%) for analyzing ethanol in octane and gasoline have been demonstrated by leveraging colorimetric sensing in both liquid and gas phases. Proof‐of‐concept tests for specifically detecting ethanol in consumer medical and healthcare products have also been demonstrated. These sensors are inexpensive, reusable, durable, and readily deployable with mobile platforms for quantitative analysis. Additionally, theoretical modeling of solvent diffusion in macroporous SMPs provides fundamental insights into the mechanisms of nanoscopic SM recovery, which is a topic that has received little examination. These novel sensors are of great technological importance in a wide spectrum of applications ranging from environmental monitoring and workplace hazard identification to threat detection and process/product control in chemical, petroleum, and pharmaceutical industries.     

A reliable decision support system for fresh food supply chain management

The paper proposes a decision support system (DSS) for the supply chain of packaged fresh and highly perishable products. The DSS combines a unique tool for sales forecasting with order planning which includes an individual model selection system equipped with ARIMA, ARIMAX and transfer function forecasting model families, the latter two accounting for the impact of prices. Forecasting model parameters are chosen via two alternative tuning algorithms: a two-step statistical analysis, and a sequential parameter optimisation framework for automatic parameter tuning. The DSS selects the model to apply according to user-defined performance criteria. Then, it considers sales forecasting as a proxy of expected demand and uses it as input for a multi-objective optimisation algorithm that defines a set of non-dominated order proposals with respect to outdating, shortage, freshness of products and residual stock. A set of real data and a benchmark – based on the methods already in use – are employed to evaluate the performance of the proposed DSS. The analysis of different configurations shows that the DSS is suitable for the problem under investigation; in particular, the DSS ensures acceptable forecasting errors and proper computational effort, providing order plans with associated satisfactory performances.     

Integrated Approach for Supporting Sustainable Water Resources Management of Irrigation Based on the WEFN Framework

Irrigated agriculture plays a vital role for the socio-economic development of the Mediterranean area, although it has significant impacts on both water and energy resources. Therefore, in a context in which water resources are also experiencing increasing pressures, there is an urgent need for supporting their sustainable management. This may be an extremely challenging task, especially at the local scale, due to the several interconnected dynamics affecting the state of a complex irrigation system. In fact, multiple actors are involved in decision-making processes, and the use of natural resources (and their mutual interactions) strongly depends on their behaviors, which affect the system as a whole. In this context, the present study proposes an integrated methodology, based on the Water Energy Food Nexus (WEFN), specifically focused on the sustainable management of water resources for irrigation. Firstly, a model based on Causal Loop Diagrams (CLD) is developed in order to get a deep insight into the key dynamics behind a complex irrigation system. Secondly, three indices based on the “footprint” concept are identified, in order to synthesize such dynamics. The integration of these two approaches support investigating the whole system and, particularly, understanding the influence of multiple decisional actors on it, as well as the role of a set of key drivers and constraints. This might also allow drawing some relevant conclusions, useful for supporting effective decisions oriented to a sustainable water resources management. Specific reference is made to a case study, the Capitanata irrigation system, located in the Southern Italy.

     

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.