Mode-specific strategy for controlling a single-molecule reaction

Inelastic tunnelling electrons are a proper excitation source to induce chemical transformations on a single adsorbate. When their energy is tuned to that of molecular vibrational states, the modification may follow complex internal vibrational pathways. Here, we analyse our recent results on the selective excitation of ammonium stretching or bending modes to control the outcome of a simple bond-cleavage reaction. With the help of model calculations, we provide a detailed molecular-scale picture of the competing internal pathways leading to molecular movement. A mode-selective strategy, based on local excitations of specific reaction coordinates, has an important drawback when applied to adsorbate systems due to the problem of fast energy randomization. The success of such a mode-selective strategy is determined here by the ability of the scanning tunnelling microscope to study reactivity in the limit of very low yield and very low power irradiation, in a regime where vibrational heating of the adsorbate/surface system becomes negligible.     

Modeling of zinc solubility in stabilized/solidified electric arc furnace dust

Equilibrium models which attempt for the influence of pH on the solubility of metals can improve the dynamic leaching models developed to describe the long-term behavior of waste-derived forms. In addition, such models can be used to predict the concentration of metals in equilibrium leaching tests at a given pH. The aim of this work is to model the equilibrium concentration of Zn from untreated and stabilized/solidified (S/S) electric arc furnace dust (EAFD) using experimental data obtained from a pH-dependence leaching test (acid neutralization capacity, ANC). EAFD is a hazardous waste generated in electric arc furnace steel factories; it contains significant amounts of heavy metals such as Zn, Pb, Cr or Cd. EAFD from a local factory was characterized by X-ray fluorescence (XRF), acid digestion and X-ray diffraction (XRD). Zn and Fe were the main components while the XRD analysis revealed that zincite, zinc ferrite and hematite were the main crystalline phases. Different cement/EAFD formulations ranging from 7 to 20% dry weight of cement were prepared and subjected to the ANC leaching test. An amphoteric behavior of Zn was found from the pH dependence test. To model this behavior, the geochemical model Visual MINTEQ (VMINTEQ) was used. In addition to the geochemical model, an empirical model based on the dissolution of Zn in the acidic zone and the re-dissolution of zinc compounds in the alkaline zone was considered showing a similar prediction than that obtained with VMINTEQ. This empirical model seems to be more appropriate when the metal speciation is unknown, or when if known, the theoretical solid phases included in the database of VMINTEQ do not allow to describe the experimental data.     

Guidance of a mobile robot using an array of static cameras located in the environment

This paper presents a new proposal for positioning and guiding mobile robots in indoor environments. The proposal is based on the information provided by static cameras located in the movement environment. This proposal falls within the scope of what are known as intelligent environments; in this case, the environment is provided with cameras that, once calibrated, allow the position of the robots to be obtained. Based on this information, control orders for the robots can be generated using a radio frequency link. In order to facilitate identification of the robots, even under extremely adverse ambient lighting conditions, a beacon consisting of four circular elements constructed from infrared diodes is mounted on board the robots. In order to identify the beacon, an edge detection process is carried out. This is followed by a process that, based on the algebraic distance, obtains the estimated ellipses associated with each element of the beacon. Once the beacon has been identified, the coordinates of the centroids for the elements that make up the beacon are obtained on the various image planes. Based on these coordinates, an algorithm is proposed that takes into account the standard deviation of the error produced in the various cameras in ascertaining the coordinates of the beacon’s elements. An odometric system is also used in guidance that, in conjunction with a Kalman Filter, allows the position of the robot to be estimated during the time intervals required to process the visual information provided by the cameras.

Genetic algorithm to design logical topologies in reconfigurable WDM networks

A new method to design logical topologies based on genetic algorithms is presented. Not only does the algorithm determine which nodes should be connected by means of lightpaths with the aim of minimizing congestion, but it also solves the routing and wavelength assignment problem. In this way, the algorithm guarantees that the logical topology obtained can be embedded in the optical network subject to the available set of resources. The algorithm is effective in terms of both congestion and fairness. For instance, when compared with other work, the congestion is significantly reduced (from 20% to 75% depending on the matrix of traffic considered), and the fairness, when evaluated in terms of the Jain index, is generally higher than 0.94. Moreover, the algorithm brings advantages when employed in dynamic scenarios where the logical topology is frequently reconfigured, as it is fast and, in contrast to other algorithms previously proposed, the calculation process can be stopped at any time (if required) in order to give the best virtual topology found up to the moment.

A computer implementation of the partition of the unity procedure and its application to arthropod population dynamics. A case study on the European grape berry moth

This paper presents a new procedure to construct families of spatial approximation-prediction functions which depend on several parameters. The method is based on partitions of the unity. In order to find optimal functions in these families we introduce a Vietoris simplicial set associated to an influence radius. We consider error estimators induced by these Vietoris simplicial sets. A computational implementation of these mathematical models has been developed to be applied to any kind of finite discrete data. Our methods provide a useful tool for the analysis of the spatial distribution of species, which is imperative for developing accurate and efficient management of endangered and invasive species, biological conservation programs, etc. We demonstrate the application of our method to the analysis of the spatial distribution of the grape moth Lobesia botrana (Lepidoptera: Tortricidae) in the vineyards of La Rioja obtaining useful results for the management of this pest.     

Magnetic interactions as a stabilizing factor of semiquinone species of lawsone by metal complexation

Changes in electrochemical reactivity for lawsone anions (lawsone, 2-hydroxy-1,4-naphthoquinone, HLw) being coordinated to a series of metallic ions in dimethylsulfoxide solution were evaluated. Upon performing cyclic voltammetry experiments for metal complexes of this quinone with pyridine (Py) - structural formula M(II)(Lw⁻)₂(Py)₂; M: Co(II), Ni(II), Zn(II) - it was found that the reduction of coordinated Lw⁻ units occurs during the first and second electron uptake in the analyzed compounds. The stability of the electrogenerated intermediates for each complex depends on the d electron configuration in each metal center and is determined by magnetic interactions with the available spins considering an octahedral conformation for all the compounds. This was evidenced by in situ spectroelectrochemical-ESR measurements in the Zn(II) complex in which due to the lack of magnetic interaction owing to its electron configuration, the structure of the coordinated anion radical species was determined. Successive reduction of the associated Lw⁻ units leads to partial dissociation of the complex, determined by the identification of free radical dianion structures in solution. These results show some insights on how metal-lawsone complexation can modify the solution reactivity and stability of the electrogenerated radical species.     

The effects of the number of links and navigation support on cognitive load and learning with hypertext: The mediating role of reading order

Problems in learning with hypertext systems have been claimed to be caused by high levels of disorientation and cognitive load. This was recognized by DeStefano and LeFevre [DeStefano, D., & LeFevre, J. -A., (2007). Cognitive load in hypertext reading: A review. Computers in Human Behavior, 23(3), 1616–1641.] who predicted an increase of cognitive load and impairment of learning for hypertexts with a higher number of links per page. From a practical perspective, several navigation support techniques, such as providing link suggestions, have been proposed for guiding learners and reducing cognitive overload. In an experiment, we tested DeStefano and LeFevre’s predictions as well as the usefulness of link suggestions. Participants used different versions of a hypertext, either with 3-links or 8-links per page, presenting link suggestions or not. We tested their cognitive load and learning outcomes. Results showed that there was a benefit of using link suggestions for learning, but no effect of number of links on learning was found. Moreover, the effects of our manipulations on cognitive load were mediated by the reading order that participants selected. Implications for research and the design of navigation support systems are discussed.     

Techno-economic analysis of MJ class high temperature Superconducting Magnetic Energy Storage(SMES) systems applied to renewable power grids

High temperature Superconducting Magnetic Energy Storage(SMES) systems can exchange energy with substantial renewable power grids in a small period of time with very high efficiency. Because of this distinctive feature, they store the abundant wind power when the power network is congested and release the energy back to the system when there is no congestion. However, considering the cost and lifespan of SMES systems, there is an urgent demand to conduct a cost-benefit analysis to justify its role in smart grid development. This study explores the application and performs economic analysis of a 5 MJ SMES in a practical renewable power system in China based on the PSCAD/EMTDC software. An optimal location of SMES in Zhangbei wind farm is presented using real power transmission parameters. The stabilities of the renewable power grid with and without SMES are discussed. In addition, a financial feasibility study is conducted by comparing the cost and the savings from wind power curtailment of deploying SMES and battery. The economic analysis tries to find the balance between SMES investment cost and wind farm operation cost by using real data over a calendar year. The technical analysis can help guide the optimal allocation of SMES for compensating power system instability with substantial wind power. Further, the economic analysis provides a useful indication of its practical application feasibility to fight the balance between cost and benefit.     

New cardo silylated poly(azomethine)s containing 9,9′‐diphenylfluorene units as materials with Brønsted acid‐dependent fluorescence

Aromatic poly(azomethine)s have been studied due to their attractive properties such as high thermal stability, semiconducting behavior and the ability to coordinate species with their imine units (C?N). In this paper, the synthesis and characterization of two novel silylated poly(azomethine)s containing cardo units are reported. These materials were highly soluble in organic solvents such as chloroform and m‐cresol and were thermally stable, and PAzMC1 exhibited a high glass transition temperature value (287 °C), while that for PAzMC2 was not observed. UV–visible spectrophotometry revealed absorption bands related to the aromatic backbone of both PAzMCs, 300–285 nm in tetrahydrofuran and 310–301 nm in dimethylsulfoxide, and bands attributed to the conjugated imine unit at around 350 nm. In order to investigate the phenomenon of the emission of fluorescence promoted by dopant agents with regard to potential optoelectronic applications, the materials were doped with H₂SO₄ and their optical and electrochemical properties investigated. Thus, the absorption band of the imine group was suppressed due to the nitrogen atoms being protonated. Fluorescence spectroscopy analysis developed in dilute solutions of polymers showed no emission from the undoped polymers, whereas the acid‐doped species emitted fluorescence in the UV and violet regions (322 nm). Cyclic voltammetry measurements were carried out and HOMO–LUMO energies were estimated. This study provides a starting point for the development of new poly(azomethine)s with doping‐dependent emission. © 2019 Society of Chemical Industry     

Mono‐Estolide Synthesis from trans‐8‐Hydroxy‐Fatty Acids by Lipases in Solvent‐Free Media and Their Physical Properties

Pseudomonas aeruginosa 42A2 is known to produce two hydroxy‐fatty acids, 10(S)‐hydroxy‐8(E)‐octadecenoic and 7,10(S,S)‐dihydroxy‐8(E)‐octadecenoic acids, when cultivated in a mineral medium using oleic acid as a single carbon source. These compounds were purified, 91 and 96 % respectively, to produce two new families of estolides: trans‐8‐estolides and saturated estolides from the monohydroxylated monomer. trans‐8‐estolides were produced by three different lipases (Novozym 435, Lipozyme RM IM and Lipozyme TL IM) with reaction yields between 68.4 ± 2.1 and 94.7 ± 2.4 % in a solvent‐free medium at 80 °C in 168 h under vacuum. Novozym 435 was found to be the most efficient biocatalyst for both hydroxy‐fatty acids with reaction yields of 71.7 ± 2.3 and 94.7 ± 2.4 %, respectively. Moreover, saturated estolides were also produced from a saturated 10(S)‐hydroxy‐8(E)‐octadecenoic. These estolides were chemically and enzymatically synthesized with Novozym 435, under the previous described reaction conditions with yields of 60.7 ± 2.1 and 71.2 ± 2.3 % respectively. Finally, viscosity, glass transition temperature, decomposition temperatures and enthalpies were determined to characterize both types of estolides. Thermal applications for both types of polyesters were improved since glass transition temperatures were lowered and decomposition temperatures were increased, with respect to their corresponding substrates.