Novel initiators for the synthesis of propylene oxide oligomers by anionic ring opening polymerization

A series of potassium alcoholates was obtained from the reaction between KOH and ethylene glycol, resorcinol, 4,4′-bisphenol A, 4,4′-(1,3 phenylenediisopropylidene)-bisphenol, 4,4′-sulfonyldiphenol. These salts were employed to initiate the anionic ring opening polymerization of propylene oxide (PO). The molecular weight distribution of the propylene oxide oligomers prepared by this method and the initiator structure were correlated. These oligomers were characterized through Fourier transform infrared (FTIR), nuclear magnetic resonance (NMR) spectroscopies and size exclusion chromatography (SEC). It was found that the molecular weight and polydispersity of the synthesized poly(propylene oxide) (PPO) is highly dependant on the initiator structure and solubility in the reactive medium. The oligomers obtained using di-potassium resorcinolate exhibited a molecular weight distribution more polydisperse than that of PO oligomers synthesized by means of di-potassium ethylene glycolate. In the case of the PO polymerizations started by the potassium salts of 4,4′-bisphenol A, 4,4′-(1,3 phenylenediisopropylidene)-bisphenol and 4,4′-sulfonyldiphenol, the oligomer chains showed very broad molecular weight distributions. In general, lower solubility and augmentation of the polymer polydispersity were observed when the number of aromatic rings in the initiator structure increased. The experimental results were contrasted with those obtained from quantum chemical semiempirical calculations at AM1 level. The peculiar behavior exhibited by the initiators with an aromatic structure could be explained in terms of different reactivities of the initiation sites. The theoretical studies revealed that the ring in the aromatic initiators promotes an unsymmetrical growing when the PPO chains are formed. In contrast, the identical reactivity of both initiation sites in the ethylene glycolate produces a symmetrical growing during the PO polymerization.     

Charge transport in disordered graphene-based low dimensional materials

Two-dimensional graphene, carbon nanotubes, and graphene nanoribbons represent a novel class of low dimensional materials that could serve as building blocks for future carbon-based nanoelectronics. Although these systems share a similar underlying electronic structure, whose exact details depend on confinement effects, crucial differences emerge when disorder comes into play. In this review, we consider the transport properties of these materials, with particular emphasis on the case of graphene nanoribbons. After summarizing the electronic and transport properties of defect-free systems, we focus on the effects of a model disorder potential (Anderson-type), and illustrate how transport properties are sensitive to the underlying symmetry. We provide analytical expressions for the elastic mean free path of carbon nanotubes and graphene nanoribbons, and discuss the onset of weak and strong localization regimes, which are genuinely dependent on the transport dimensionality. We also consider the effects of edge disorder and roughness for graphene nanoribbons in relation to their armchair or zigzag orientation. This article is published with open access at Springerlink.com     

Discrimination of isotrigon textures using the Rényi entropy of Allan variances

We present a computational algorithm for isotrigon texture discrimination. The aim of this method consists in discriminating isotrigon textures against a binary random background. The extension of the method to the problem of multitexture discrimination is considered as well. The method relies on the fact that the information content of time or space-frequency representations of signals, including images, can be readily analyzed by means of generalized entropy measures. In such a scenario, the Rényi entropy appears as an effective tool, given that Rényi measures can be used to provide information about a local neighborhood within an image. Localization is essential for comparing images on a pixel-by-pixel basis. Discrimination is performed through a local Rényi entropy measurement applied on a spatially oriented 1-D pseudo-Wigner distribution (PWD) of the test image. The PWD is normalized so that it may be interpreted as a probability distribution. Prior to the calculation of the texture's PWD, a preprocessing filtering step replaces the original texture with its localized spatially oriented Allan variances. The anisotropic structure of the textures, as revealed by the Allan variances, turns out to be crucial later to attain a high discrimination by the extraction of Rényi entropy measures. The method has been empirically evaluated with a family of isotrigon textures embedded in a binary random background. The extension to the case of multiple isotrigon mosaics has also been considered. Discrimination results are compared with other existing methods.     

Modeling and improving the logistic distribution network of a hospital

This paper discusses using simulation and optimization to improve the hospital‐internal distribution network, for example, how to schedule and deliver the goods, which items should go on which cart, how to manage the variable consumption in the units, etc. We use a real case to build a simulation model to test various processes and incorporate an optimization algorithm to find the best distribution routes. The results highlight concrete improvements that could be made. These are the use of the same cart for different types of supplies to reduce the number of routes, the reduction of the distribution frequency for certain care units, and the use of optimized routes to reduce the transportation time.     

Prognostic and Predictive Factors in Advanced Head and Neck Squamous Cell Carcinoma

Head and neck squamous cell carcinoma (HNSCC) is a heterogeneous disease arising from the mucosa of the upper aerodigestive tract. Despite multimodality treatments approximately half of all patients with locally advanced disease relapse and the prognosis of patients with recurrent or metastatic HNSCC is dismal. The introduction of checkpoint inhibitors improved the treatment options for these patients and pembrolizumab alone or in combination with a platinum and fluorouracil is now the standard of care for first-line therapy. However, approximately only one third of unselected patients respond to this combination and the response rate to checkpoint inhibitors alone is even lower. This shows that there is an urgent need to improve prognostication and prediction of treatment benefits in patients with HNSCC. In this review, we summarize the most relevant risk factors in the field and discuss their roles and limitations. The human papilloma virus (HPV) status for patients with oropharyngeal cancer and the combined positive score are the only biomarkers consistently used in clinical routine. Other factors, such as the tumor mutational burden and the immune microenvironment have been highly studied and are promising but need validation in prospective trials.     

Enhanced activity of Pd/α-MnO2 for electrocatalytic oxygen evolution reaction

This work describes the application of α-MnO₂ and Pd/α-MnO₂ as electrocatalysts in the oxygen evolution reaction (OER). Characterization data revealed that the Pd²⁺ precursor has been oxidized during the synthesis, and the resulting Pd⁴⁺ ions have unprecedently replaced the lattice framework Mn³⁺ ions of α-MnO₂. Furthermore, formation of PdO nanoparticles was also observed. Lower OER overpotential at j = 10 mA cm^?2 (636 mV) was obtained for Pd/α-MnO₂ in relation to α-MnO₂ (700 mV), what is in alignment with the lower charge transfer resistance of Pd/α-MnO₂ (4.9 kΩ cm²) compared to α-MnO₂ (10.4 kΩ cm²). Lower Tafel slope (73 mV dec^?1) and higher TOF (2.87 × 10^?4 s^?1) at overpotential of 350 mV was obtained for Pd/α-MnO₂ in relation to α-MnO₂ (Tafel of 77 mV dec^?1 and TOF of 1.94 × 10^?4 s^?1), indicating a faster electron transfer kinetics promoted by Pd. Pd/α-MnO₂ was stable at j = 14 mA cm^?2 for 6 h.     

Evaluation of interfacial pH change during water splitting at pulsed regime using finite element method

Electrochemical water splitting is a well-known reaction, investigated since 1869 due to its wide applicability for different purposes. Despite occurring at the electrode/solution interface, this set of reactions can be governed not only by interfacial properties but also by reactant transport from the solution toward the electrode surface. For water splitting specifically, the reaction mechanism itself leads to a pH change at the interface although the bulk value remains constant. In this work, we simulated such pH variations using the finite element method. The results show an interfacial pH change of up to 9 pH units. This modification in the reaction condition affects many related parameters such as electric power consumption, which increases. Thence, we investigated the effect of using an AC perturbation. In the conditions we have studied, it is observed an important delay in the pH change, although it always occurs.     

Hydrogen storage properties of new A3B2-type TiZrNbCrFe high-entropy alloy

Crystal structure and hydrogen storage properties of a novel equiatomic TiZrNbCrFe high-entropy alloy (HEA) were studied. The selected alloy, which had a A₃B₂-type configuration (A: elements forming hydride, B: elements with low chemical affinity with hydrogen) was designed to produce a hydride with a hydrogen-to-metal atomic ratio (H/M) higher than those for the AB₂- and AB-type alloys. The phase stability of alloy was investigated through thermodynamic calculations by the CALPHAD method. The alloy after arc melting showed the dominant presence of a solid solution C14 Laves phase (98.4%) with a minor proportion of a disordered BCC phase (1.6%). Hydrogen storage properties investigated at different temperatures revealed that the alloy was able to reversibly absorb and fully desorb 1.9 wt% of hydrogen at 473 K. During the hydrogenation, the initial C14 and BCC crystal structures were fully converted into the C14 and FCC hydrides, respectively. The H/M value was 1.32 which is higher than the value of 1 reported for the AB₂- and AB-type HEAs. The present results show that good hydrogen storage capacity and reversibility at moderate temperatures can be attained in HEAs with new configurations such as A₃B₂/A₃B₂H₇.     

Extremophile microalgae as feedstock for high-value carotenoids: A review

There are places in our planet where environmental conditions are beyond normal limits for growth but still harbour life. Extremophile microalgae are the candidates for large-scale production because (i) their extreme growth conditions help to avoid unwanted contaminations, facilitating their production and (ii) in order to survive under harsh environments, these microorganisms synthesise valuable uncommon biomolecules. Extremophile microalgae include Arthrospira platensis, used as a source of phycocyanin and produced under highly alkaline conditions, and Dunaliella salina, which is industrially produced as a source of β-carotene and can naturally resist salinity conditions exceeding 300 g L⁻¹. Microalgae can be produced on non-arable lands, using seawater, and within a wide range of environmental conditions, allowing their production in almost any part of the planet. The current paper aimed at highlighting the biotechnological potential of extremophile microalgae as sources for carotenoids, valuable molecules used as pigments and health-promoters.