Electrochemical comparison and deposition of lithium and potassium from phosphonium- and ammonium-tfsi ionic liquids

In this work, ionic liquids (ILs) were investigated for use as battery electrolytes. The ILs were synthesized from quaternary ammonium and phosphonium salts and TFSI-. A dendrite free lithium metal anode was demonstrated by deposition of a lithium-potassium alloy. Several phosphonium ILs were synthesized using the TFSI- and PF6- anions until a room temperature IL was obtained. The smaller size, highly symmetric PF6- anion yielded high melting point salts, while TFSI- yielded much lower melting point ILs. When a room temperature IL, Bu3HexP+TFSI-, was obtained the analogous ammonium IL, Bu3HexP+TFSI-, was synthesized and compared. The phosphonium-based ionic liquid showed improved stability and physical properties compared to the analogous ammonium-based IL. The phosphonium-based IL had higher conductivity, 0.43 mS/cm, than the ammonium-based IL, 0.28 mS/cm. The addition of LiTFSI to both ILs led to a decrease in conductivity and increase in viscosity. The lower viscosity and higher stability of the phosphonium-based IL led to higher current density and stability for electrodeposited lithium metal. IL reduction interfered with lithium deposition reflecting lower coulombic efficiencies and giving the appearance of an unstable lithium couple. An optimum deposition potential was found which was bounded by the electrochemical stability of each IL. The stability of lithium in the ILs increased at lower temperature due to slower reactivity with the IL. Addition of higher quantities of lithium ions caused a higher fraction of the cathodic current going to lithium deposition that was reoxidized. The stability of lithium in the ILs increased at lower temperature due to slower reactivity with the IL. The electrodeposition and reoxidation of potassium was also demonstrated. Deposition of a lithium-potassium alloy caused slight increases in the cathodic and anodic currents along with higher coulombic efficiencies. Also, it was found that a lithium-potassium alloy could be deposited at high current for long times without the occurrence of dendrites.M.S.Committee Chair: Paul Kohl; Committee Member: Jiri Janata; Committee Member: Tom Fulle

Direct Hydroxylation of Phenol to Dihydroxybenzenes by H2O2 and Fe-based Metal-Organic Framework Catalyst at Room Temperature

A semi-crystalline iron-based metal-organic framework (MOF), in particular Fe-BTC, that contained 20 wt.% Fe, was sustainably synthesized at room temperature and extensively characterized. Fe-BTC nanopowders could be used as an efficient heterogeneous catalyst for the synthesis of dihydroxybenzenes (DHBZ), from phenol with hydrogen peroxide (H2O2), as oxidant under organic solvent-free conditions. The influence of the reaction temperature, H2O2 concentration and catalyst dose were studied in the hydroxylation performance of phenol and MOF stability. Fe-BTC was active and stable (with negligible Fe leaching) at room conditions. By using intermittent dosing of H2O2, the catalytic performance resulted in a high DHBZ selectivity (65%) and yield (35%), higher than those obtained for other Fe-based MOFs that typically require reaction temperatures above 70◦C. The long-term experiments in a fixed-bed flow reactor demonstrated good Fe-BTC durability at the above conditionsThe authors thank the financial support by Consejo Nacional de Ciencia y Tecnología (CONACYT) for the grant number 764635 and the project 256296; and to TNM for the supporting project 5627.19.P. Also, to the Spanish Ministerio de Ciencia, Innovación y Universidades (MICINN) and FEDER program (EU) through the projects: CTM2016-76454-R (MICINN) and RTI2018-095052-B-I00 ((MCIU/AEI/FEDER, UE

Event-triggered attitude control for flying robots using an event approach based on the control

International audienceThis paper presents the development of a quaternion-based nonlinear event-triggered control for the attitude stabilization of Flying robots. Firstly, it is proved the existence of a Control Lyapunov Function. Unlike some previously proposed schemes, the aim of this paper is to propose a new and simpler event function. The control law ensures the asymptotic stability of the closed-loop system to the desired attitude. The approach is validated in real-time using a quadrotor mini-helicopter. The experiments show that the event driven controller reduces the control update without deteriorating the closed-loop system performance

Regulation of gap junction channels and hemichannels by phosphorylation

Post-translational modifications of connexins play an important role in the regulation of gap junction and hemichannel permeability. The prerequisite for the formation of functional gap junction channels is the assembly of connexin proteins into hemichannels and their insertion into the membrane. Hemichannels can affect cellular processes by enabling the passage of signaling molecules between the intracellular and extracellular space. For the intercellular communication hemichannels from one cell have to dock to its counterparts on the opposing membrane of an adjacent cell to allow the transmission of signals via gap junctions from one cell to the other. The controlled opening of hemichannels and gating properties of complete gap junctions can be regulated via post-translational modifications of connexins. Not only channel gating, but also connexin trafficking and assembly into hemichannels can be affected by post-translational changes. Recent investigations have shown that connexins can be modified by phosphorylation/ dephosphorylation, redox-related changes including effects of nitric oxide (NO), hydrogen sulfide (H2S) or carbon monoxide (CO), acetylation, methylation or ubiquitination. Most of the connexin isoforms are known to be phosphorylated, e.g. Cx43, one of the most studied connexin at all, has 21 reported phosphorylation sites. In this review, we provide an overview about the current knowledge and relevant research of responsible kinases, connexin phosphorylation sites and reported effects on gap junction and hemichannel regulation. Regarding the effects of oxidants we discuss the role of NO in different cell types and tissues and recent studies about modifications of connexins by CO and H2S

Regulation of gap junction channels and hemichannels by phosphorylation

Post-translational modifications of connexins play an important role in the regulation of gap junction and hemichannel permeability. The prerequisite for the formation of functional gap junction channels is the assembly of connexin proteins into hemichannels and their insertion into the membrane. Hemichannels can affect cellular processes by enabling the passage of signaling molecules between the intracellular and extracellular space. For the intercellular communication hemichannels from one cell have to dock to its counterparts on the opposing membrane of an adjacent cell to allow the transmission of signals via gap junctions from one cell to the other. The controlled opening of hemichannels and gating properties of complete gap junctions can be regulated via post-translational modifications of connexins. Not only channel gating, but also connexin trafficking and assembly into hemichannels can be affected by post-translational changes. Recent investigations have shown that connexins can be modified by phosphorylation/ dephosphorylation, redox-related changes including effects of nitric oxide (NO), hydrogen sulfide (H2S) or carbon monoxide (CO), acetylation, methylation or ubiquitination. Most of the connexin isoforms are known to be phosphorylated, e.g. Cx43, one of the most studied connexin at all, has 21 reported phosphorylation sites. In this review, we provide an overview about the current knowledge and relevant research of responsible kinases, connexin phosphorylation sites and reported effects on gap junction and hemichannel regulation. Regarding the effects of oxidants we discuss the role of NO in different cell types and tissues and recent studies about modifications of connexins by CO and H2S

Event-triggered attitude control for flying robots using an event approach based on the control

International audienceThis paper presents the development of a quaternion-based nonlinear event-triggered control for the attitude stabilization of Flying robots. Firstly, it is proved the existence of a Control Lyapunov Function. Unlike some previously proposed schemes, the aim of this paper is to propose a new and simpler event function. The control law ensures the asymptotic stability of the closed-loop system to the desired attitude. The approach is validated in real-time using a quadrotor mini-helicopter. The experiments show that the event driven controller reduces the control update without deteriorating the closed-loop system performance

Non-Markovian Stochastic Resonance: three state model of ion channel gating

Stochastic Resonance in single voltage-dependent ion channels is investigated within a three state non-Markovian modeling of the ion channel conformational dynamics. In contrast to a two-state description one assumes the presence of an additional closed state for the ion channel which mimics the manifold of voltage-independent closed subconformations (inactivated ``state''). The conformational transition into the open state occurs through a domain of voltage-dependent closed subconformations (closed ``state''). At distinct variance with a standard two-state or also three-state Markovian approach, the inactivated state is characterized by a broad, non-exponential probability distribution of corresponding residence times. The linear response to a periodic voltage signal is determined for arbitrary distributions of the channel's recovery times. Analytical results are obtained for the spectral amplification of the applied signal and the corresponding signal-to-noise ratio. Alternatively, these results are also derived by use of a corresponding two-state non-Markovian theory which is based on driven integral renewal equations [I. Goychuk and P. Hanggi, Phys. Rev. E 69, 021104 (2004)]. The non-Markovian features of stochastic resonance are studied for a power law distribution of the residence time-intervals in the inactivated state which exhibits a large variance. A comparison with the case of bi-exponentially distributed residence times possessing the same mean value, i.e. a simplest non-Markovian two-state description, is also presented

Structured reactors based on 3D Fe/SiC Catalysts: understanding the effects of mixing

The application of structured reactors provides a number of advantages in chemical processes. In this paper, two different three-dimensional (3D) Fe/SiC catalysts with a square cell geometry have been manufactured by Robocasting: monoliths (D = 14 and H = 15 mm) and meshes (D = 24 and H = 2 mm) and studied in the catalytic phenol oxidation by hydrogen peroxide (H2O2) for the sustainable production of dihydroxybenzenes (DHBZ). The fluid dynamics, catalytic performance, reaction rates, external mass transport limitation, and catalyst stability have been compared in three different reactors, monolithic fixed-bed reactor, multimesh fixed-bed reactor, and monolithic stirrer reactor, at selected operating conditions. The results show that the mechanical stirring of the 3D Fe/SiC monoliths avoids the external mass transfer limitation caused by the presence of oxygen bubbles in the channels (produced from the HOx· species in autoscavenging radical reactions). In addition, the backmixing has a positive effect on the efficient consumption of H2O2 but an adverse effect on the phenol selectivity to DHBZ since they are overoxidized to tar products at longer contact times. On the other hand, the wall porosity, and not the backmixing, affects the susceptibility of the 3D Fe/SiC catalyst to the Fe leaching, as occurs in the mesh structures. In conclusion, the monoliths operating under plug-flow and external mass transfer limitation in the monolithic fixed-bed reactor (MFB) provide an outstanding phenol selectivity to DHBZ and catalyst stabilityThis work is supported by the following agencies and grants: the Spanish Government under projects RTI2018-095052-BI00 (MICINN/AEI/FEDER, UE) and EIN2020-112153 (MCINN/AEI/10.13039/501100011033), the latter was also supported by the European Union through “NextGenerationEU/PRTR”, Community of Madrid under project S2018/ EMT-4341, and CSIC project I-COOP+ 2019 (ref COOPB20405). P.L. acknowledges the Community of Madrid and the European Social Fund for the financial support received through the contract PEJ-2019-AI/IND-14385. The authors thank Juliana Mejía for her technical assistanc

Innovation as competitiveness driving force through the resources and capacities of SMEs in Costa Rica, Puerto Rico, and Dominican Republic

Literature reflects that Latin America and the Caribbean register more SMEs and produce more entrepreneurial activity than any other place in the world. Using the Theory of Resources and Capabilities, this research explored how SMEs in Costa Rica, Puerto Rico, and the Dominican Republic managed the heterogeneity of their entrepreneurial orientation, market orientation, social and human capital resources and their impact on innovation capacity and competitiveness. With a survey of 467 SMEs and the analysis of data with the use of PLS-SEM & PLS-MGA, this study contributed new information based on resources and capacities that showed the maximum set of possible variables analyzed for a theoretical understanding and practice of the heterogeneity of resources. The results reflected a positive impact on the proposed hypothesis through the structural model. The data highlight market orientation as the most valuable resource that facilitates innovation and competitiveness in SMEs analyzed. The results revealed and contributed to the new lines of research on how differences and the degree of importance in managing resources generated high competitiveness through their capacity for innovation

Coccidioides immitis presenting with acute hydropneumothorax in an immunocompetent patient from South Texas

Coccidioidomycosis is a disease caused by the dimorphic fungi Coccidioides immitis and Coccidioides posadasii that predominates in dry climates and it is endemic in Southern California and Arizona. Coccidioides is also found in parts of West Texas and a long the Rio Grande River, however, incidence tends to decrease in areas close to the Gulf of Mexico due to increased humidity. Coccidioidomycosis is more commonly a subclinical and self-limited disease in up to sixty percent of cases. Acute pneumonia (Valley fever), extra thoracic disseminated infection and complications occur more frequently in immunocompromised hosts. We present a case of severe coccidiomycosis in an immunocompetent host who lived in central California for two months, 2 years prior to manifesting severe respiratory compromise. Clinicians should be able to recognize differential diagnoses for cavitary-like lung lesions, paying close attention to social history and CDC epidemiology data