Ab initio study of the CE magnetic phase in half-doped manganites: Purely magnetic versus double exchange description

The leading electronic interactions governing the local physics of the CE phase of half-doped manganites are extracted from correlated ab initio calculations performed on an embedded cluster. The electronic structure of the low-energy states is dominated by double exchange configurations and O-2$p_{\sigma}$ to Mn-3d charge transfer configurations. The model spectra of both a purely magnetic non-symmetric Heisenberg Hamiltonian involving a magnetic oxygen and two non-symmetric double exchange models are compared to the \textit{ab initio} one. While a satisfactory agreement between the Heisenberg spectrum and the calculated one is obtained, the best description is provided by a double exchange model involving excited non-Hund atomic states. This refined model not only perfectly reproduces the spectrum of the embedded cluster in the crystal geometry, but also gives a full description of the local double-well potential energy curve of the ground state (resulting from the interaction of the charge localized electronic configurations) and the local potential energy curves of all excited states ruled by the double exchange mechanism

Is Microtox® toxicity related to potentially harmful algae proliferation in Mediterranean salt marshes?

Is Microtox® toxicity related to potentially harmful algae proliferation in Mediterranean salt marshes? Mediterranean salt marshes are ecosystems that are highly influenced by sea changes and freshwater inputs from runoff. In these ecosystems, toxic and nontoxic algae blooms often produce Jarge and unpredictabJe biomasses of phytoplankton. The Microtox@) test has been described as a successful, quick method for detecting toxicity in various phytoplankton taxa. Our study sought to test the efficiency of Microtox® in detecting toxic HAB in Mediterranean salt marshes. The results showed that the Microtox® test was able to detect toxic substances in the particulate matter of several lagoons in the Emporda salt marshes. This Microtox® toxicity coincided with periods when potentially harrnful cyanobacteria, dinoflagellates and haptophytes had a high biomass. The results suggest that potentially harmful phytoplankton cannot be ruled out as a source of Microtox® toxicity or as a source of other organism kills and subacute effects in Mediterranean salt marshes.Las marismas mediterráneas son ecosistemas altamente injluenciados por la entrada de agua marina y de agua dulce, procedente de la escorrentía. En estos ecosistemas, las proliferaciones de algas tóxicas y no tóxicas sin patrón temporal o espacial, alcanzan altas e impredecibles biomasas de fitoplancton. El ensayo Microtox® ha sido descrito como un rápido y eficiente método para detectar la toxicidad de diferentes taxones de fitoplaneton. Nosotros hemos hecho una primera aproximación para determinar la eficiencia del test Microtox® en la detección de proliferaciones algales tóxicas en las marismas mediterráneas. Se ha podido concluir que hay substancias tóxicas, en la materia particulada de diversas lagunas de las marismas del Emporda, que el método Microtox® es capaz de detectar. Esta toxicidad detectada por Microtox® se da en periodos en que cianobacterias, dinojlagelados y haptófitos potencialmente tóxicos presentan alta biomasa. Los resultados sugieren que el fitoplancton potencialmente tóxico no puede ser descartado como causante de la mortalidad o de efectos subagudos a otros organismos de las marismas mediterráneas

A theoretical study of the low-lying excited states of thieno[3,4-b]pyrazine

The low-lying electronic excited states of thieno[3,4-b]pyrazine have been studied using the multiconfigurational second-order perturbation CASPT2 theory with extended atomic natural orbital basis sets. The CASPT2 results allow for a full interpretation of the electronic absorption and emission spectra and provide valuable information for the rationalization of the experimental data. The nature, position, and intensity of the spectral bands have been analyzed in detail. A preliminary comparative study of the ground-state geometry of thieno[3,4-b]pyrazine has been performed at the coupled cluster single and doubles and density functional theory levels using a variety of correlation-consistent basis sets. Thieno[3,4-b]pyrazine exhibits a polyene-like structure in the ground state due to the bond localization in the pyrazine moiety. An aromatization of the pyrazine unit is predicted for the lowest-energy electronic excited [email protected] [email protected] [email protected]

Point defects on graphene on metals

Understanding the coupling of graphene with its local environment is critical to be able to integrate it in tomorrow's electronic devices. Here we show how the presence of a metallic substrate affects the properties of an atomically tailored graphene layer. We have deliberately introduced single carbon vacancies on a graphene monolayer grown on a Pt(111) surface and investigated its impact in the electronic, structural and magnetic properties of the graphene layer. Our low temperature scanning tunneling microscopy studies, complemented by density functional theory, show the existence of a broad electronic resonance above the Fermi energy associated with the vacancies. Vacancy sites become reactive leading to an increase of the coupling between the graphene layer and the metal substrate at these points; this gives rise to a rapid decay of the localized state and the quenching of the magnetic moment associated with carbon vacancies in free-standing graphene layers

Extended Functionalities of Photovoltaic Systems with Flexible Power Point Tracking:Recent Advances

The power system is experiencing an ever-increasing integration of photovoltaic power plants (PVPPs), which leads demand on the power system operators to force new requirements to sustain with quality and reliability of the grid. Subsequently, a significant quantity of flexible power point tracking (FPPT) algorithms have been proposed in the literature to enhance functionalities PVPPs. The intention of FPPT algorithms is to regulate the PV power to a specific value imposed by the grid codes and operational conditions. This will inevitably interfere the maximum power point tracking (MPPT) operation of PV systems. Nevertheless, the FPPT control makes PVPPs much more grid-friendly. The main contribution of this paper is to comprehensively compare available FPPT algorithms in the literature from different aspects and provide a benchmark for researchers and engineers to select suitable FPPT algorithms for specific applications. A classification and short description of them are provided. The dynamic performances of the investigated algorithms are compared with experimental tests on a scaled-down prototype. Directions for future studies in this area are also presented.MOE (Min. of Education, S’pore)Accepted versio

Surface-controlled reversal of the selectivity of halogen bonds

Intermolecular halogen bonds are ideally suited for designing new molecular assemblies because of their strong directionality and the possibility of tuning the interactions by using different types of halogens or molecular moieties. Due to these unique properties of the halogen bonds, numerous areas of application have recently been identified and are still emerging. Here, we present an approach for controlling the 2D self-assembly process of organic molecules by adsorption to reactive vs. inert metal surfaces. Therewith, the order of halogen bond strengths that is known from gas phase or liquids can be reversed. Our approach relies on adjusting the molecular charge distribution, i.e., the σ-hole, by molecule-substrate interactions. The polarizability of the halogen and the reactiveness of the metal substrate are serving as control parameters. Our results establish the surface as a control knob for tuning molecular assemblies by reversing the selectivity of bonding sites, which is interesting for future applications

Grid-Connected Energy Storage Systems: State-of-the-Art and Emerging Technologies

High penetration of renewable energy resources in the power system results in various new challenges for power system operators. One of the promising solutions to sustain the quality and reliability of the power system is the integration of energy storage systems (ESSs). This article investigates the current and emerging trends and technologies for grid-connected ESSs. Different technologies of ESSs categorized as mechanical, electrical, electrochemical, chemical, and thermal are briefly explained. Especially, a detailed review of battery ESSs (BESSs) is provided as they are attracting much attention owing, in part, to the ongoing electrification of transportation. Then, the services that grid-connected ESSs provide to the grid are discussed. Grid connection of the BESSs requires power electronic converters. Therefore, a survey of popular power converter topologies, including transformer-based, transformerless with distributed or common dc-link, and hybrid systems, along with some discussions for implementing advanced grid support functionalities in the BESS control, is presented. Furthermore, the requirements of new standards and grid codes for grid-connected BESSs are reviewed for several countries around the globe. Finally, emerging technologies, including flexible power control of photovoltaic systems, hydrogen, and second-life batteries from electric vehicles, are discussed in this article.This work was supported in part by the Office of Naval Research Global under Grant N62909-19-1-2081, in part by the National Research Foundation of Singapore Investigatorship under Award NRFI2017-08, and in part by the I2001E0069 Industrial Alignment Funding. (Corresponding author: Josep Pou.

Predictors of academic efficacy and dropout intention in university students: Can engagement suppress burnout?

In this study we modelled possible causes and consequences of student burnout and engagement on academic efficacy and dropout intention in university students. Further we asked, can student engagement protect against the effects of burnout? In total 4,061 university students from Portugal, Brazil, Mozambique, the United Kingdom, the United States of America, Finland, Serbia, and Macao SAR, Taiwan participated in this study. With the data collected we analyzed the influence of Social Support, Coping Strategies, and school/course related variables on student engagement and burnout using structural equation modeling. We also analyzed the effect of student engagement, student burnout, and their interaction, on Academic Performance and Dropout Intention. We found that both student engagement and burnout are good predictors of subjective academic performance and dropout intention. However, student burnout suppresses the effect of student engagement on these variables. This result has strong implications for practitioners and administrators. To prevent student dropout, it is not enough to promote student engagement-additionally, and importantly, levels of student burnout must be kept low. Other variables such as social support and coping strategies are also relevant predictors of student engagement and burnout and should be considered when implementing preventive actions, self-help and guided intervention programs for college students

Cobalt containing glass fibres and their synergistic effect on the HIF-1 pathway for wound healing applications

Introduction and Methods: Chronic wounds are a major healthcare problem, but their healing may be improved by developing biomaterials which can stimulate angiogenesis, e.g. by activating the Hypoxia Inducible Factor (HIF) pathway. Here, novel glass fibres were produced by laser spinning. The hypothesis was that silicate glass fibres that deliver cobalt ions will activate the HIF pathway and promote the expression of angiogenic genes. The glass composition was designed to biodegrade and release ions, but not form a hydroxyapatite layer in body fluid. Results and Discussion: Dissolution studies demonstrated that hydroxyapatite did not form. When keratinocyte cells were exposed to conditioned media from the cobalt-containing glass fibres, significantly higher amounts of HIF-1α and Vascular Endothelial Growth Factor (VEGF) were measured compared to when the cells were exposed to media with equivalent amounts of cobalt chloride. This was attributed to a synergistic effect of the combination of cobalt and other therapeutic ions released from the glass. The effect was also much greater than the sum of HIF-1α and VEGF expression when the cells were cultured with cobalt ions and with dissolution products from the Co-free glass, and was proven to not be due to a rise in pH. The ability of the glass fibres to activate the HIF-1 pathway and promote VEGF expression shows the potential for their use in chronic wound dressings