938 research outputs found
Robotic load balancing for mobility-on-demand systems
In this paper we develop methods for maximizing the throughput of a mobility-on-demand urban transportation system. We consider a finite group of shared vehicles, located at a set of stations. Users arrive at the stations, pickup vehicles, and drive (or are driven) to their destination station where they drop-off the vehicle. When some origins and destinations are more popular than others, the system will inevitably become out of balance: vehicles will build up at some stations, and become depleted at others. We propose a robotic solution to this rebalancing problem that involves empty robotic vehicles autonomously driving between stations. Specifically, we utilize a fluid model for the customers and vehicles in the system. Then, we develop a rebalancing policy that lets every station reach an equilibrium in which there are excess vehicles and no waiting customers and that minimizes the number of robotic vehicles performing rebalancing trips. We show that the optimal rebalancing policy can be found as the solution to a linear program. We use this solution to develop a real-time rebalancing policy which can operate in highly variable environments. Finally, we verify policy performance in a simulated mobility-on-demand environment and in hardware experiments.Singapore-MIT Alliance for Research and Technology CenterUnited States. Office of Naval Research (Grant N000140911051)National Science Foundation (U.S.) (Grant EFRI0735953
Unveiling Oxygen Redox Activity in P2-Type NaxNi0.25Mn0.68O2 High-Energy Cathode for Na-Ion Batteries
Na-ion batteries are emerging as convenient energy-storage devices for large-scale applications. Enhanced energy density and cycling stability are key in the optimization of functional cathode materials such as P2-type layered transition metal oxides. High operating voltage can be achieved by enabling anionic reactions, but irreversibility of O2â/O2nâ/O2 evolution still limits this chance, leading to extra capacity at first cycle that is not fully recovered. Here, we dissect this intriguing oxygen redox activity in Mn-deficient NaxNi0.25Mn0.68O2 from first-principles, by analyzing the formation of oxygen vacancies and dioxygen complexes at different stages of sodiation. We identify low-energy intermediates that release molecular O2 at high voltage, and we show how to improve the overall cathode stability by partial substitution of Ni with Fe. These new atomistic insights on O2 formation mechanism set solid scientific foundations for inhibition and control of this process toward the rational design of new anionic redox-active cathode materials
Breaking Symmetry Rules Enhance the Options for Stereoselective Propene Polymerization Catalysis
An example of breaking "Ewen's symmetry rule" for olefin catalysis polymerization is proposed by DFT calculations. Catalyst precursors with Cs symmetry are suggested to promote the isotactic propene polymerization by a modification of the active site geometry obtained via coordination with AlH-alkyl species in solution. The origin of stereocontrol in olefin polymerization is due to a dual mechanism dictated by the chiral catalyst. These findings may expand the toolbox for promoting stereoselective olefin polymerization by transition metal catalysts
Combined Structural, Chemometric, and Electrochemical Investigation of Vertically Aligned TiO2 Nanotubes for Na-ion Batteries
In the challenging scenario of anode materials for sodium-ion batteries, TiO2 nanotubes could represent a winning choice in terms of cost, scalability of the preparation procedure, and long-term stability upon reversible operation in electrochemical cells. In this work, a detailed physicochemical, computational, and electrochemical characterization is carried out on TiO2 nanotubes synthesized by varying growth time and heat treatment, viz. the two most significant experimental parameters during preparation. A chemometric approach is proposed to obtain a concrete and solid multivariate analysis of sodium battery electrode materials. Such a statistical approach, combined with prolonged galvanostatic cycling and density functional theory analysis, allows identifying anatase at high growth time as the TiO2 polymorph of choice as an anode material, thus creating a benchmark for sodium-ion batteries, which currently took the center stage of the research in the field of energy storage systems from renewables
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Investigating light-induced processes in covalent dye-catalyst assemblies for hydrogen production
The light-induced processes occurring in two dye-catalyst assemblies for light-driven hydrogen production were investigated by ultrafast transient absorption spectroscopy. These dyads consist of a push-pull organic dye based on a cyclopenta[1,2-b:5,4-bâ]dithiophene (CPDT) bridge, covalently linked to two different H2-evolving cobalt catalysts. Whatever the nature of the latter, photoinduced intramolecular electron transfer from the excited state of the dye to the catalytic center was never observed. Instead, and in sharp contrast to the reference dye, a fast intersystem crossing (ISC) populates a long-lived triplet excited state, which in turn non-radiatively decays to the ground state. This study thus shows how the interplay of different structures in a dye-catalyst assembly can lead to unexpected excited state behavior and might open up new possibilities in the area of organic triplet sensitizers. More importantly, a reductive quenching mechanism with an external electron donor must be considered to drive hydrogen production with these dye-catalyst assemblies. © 2020 by the authors. Licensee MDPI, Basel, Switzerland
Multimodal nonlinear imaging of atherosclerotic plaques differentiation of triglyceride and cholesterol deposits
Cardiovascular diseases in general and atherothrombosis as the most common of its individual disease entities is the leading cause of death in the developed countries. Therefore, visualization and characterization of inner arterial plaque composition is of vital diagnostic interest, especially for the early recognition of vulnerable plaques. Established clinical techniques provide valuable morphological information but cannot deliver information about the chemical composition of individual plaques. Therefore, spectroscopic imaging techniques have recently drawn considerable attention. Based on the spectroscopic properties of the individual plaque components, as for instance different types of lipids, the composition of atherosclerotic plaques can be analyzed qualitatively as well as quantitatively. Here, we compare the feasibility of multimodal nonlinear imaging combining two-photon fluorescence (TPF), coherent anti-Stokes Raman scattering (CARS) and second-harmonic generation (SHG) microscopy to contrast composition and morphology of lipid deposits against the surrounding matrix of connective tissue with diffraction limited spatial resolution. In this contribution, the spatial distribution of major constituents of the arterial wall and atherosclerotic plaques like elastin, collagen, triglycerides and cholesterol can be simultaneously visualized by a combination of nonlinear imaging methods, providing a powerful label-free complement to standard histopathological methods with great potential for in vivo application
Stepwise bending of DNA by a single TATA-box Binding Protein
The TATA-box Binding Protein (TBP) is required by all three eukaryotic RNA
polymerases for the initiation of transcription from most promoters. TBP
recognizes, binds to, and bends promoter sequences called ``TATA-boxes'' in the
DNA. We present results from the study of individual Saccharomyces cerevisia
TBPs interacting with single DNA molecules containing a TATA-box. Using video
microscopy, we observed the Brownian motion of beads tethered by short
surface-bound DNA. When TBP binds to and bends the DNA, the conformation of the
DNA changes and the amplitude of Brownian motion of the tethered bead is
reduced compared to that of unbent DNA. We detected individual binding and
dissociation events and derived kinetic parameters for the process.
Dissociation was induced by increasing the salt concentration or by directly
pulling on the tethered bead using optical tweezers. In addition to the
well-defined free and bound classes of Brownian motion, we observed another two
classes of motion. These extra classes were identified with intermediate states
on a three-step, linear binding pathway. Biological implications of the
intermediate states are discussed.Comment: Accepted for publication in: Biophysical Journa
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