Rigid Formation Control on a Sphere: A Heterogeneous System Approach.

We consider a heterogeneous multiagent system for tracking multiple targets with a rigid formation on a unit sphere, where the targets and chasing agents are governed by single-and double-integrator models, respectively. To make asymptotic rendezvous between agents and their corresponding targets, we use an autonomous system consisting of attraction forces and velocity alignments. If the target's position, velocity, and acceleration information are available, we derive a multiagent system for complete rendezvous and obtain its exponential convergence result. If we have only the location and velocity information of the targets, we provide an autonomous system for practical rendezvous and the corresponding mathematical analysis. To prove the main results, we employ frame-rotation-structure decomposition for the double-integrator model and the geometric properties of a rigid formation on a sphere. We also provide numerical simulations to confirm our mathematical results and apply them to multiagent dynamics with a rigid formation that patrols the boundary line for a certain area on the sphere.

Target Tracking Systems on a Sphere With Topographic Information.

We consider the target tracking problem on a sphere with topographic structure. For a given moving target on the unit sphere, we suggest a double-integrator autonomous system of multiple agents that track the given target under the topographic influence. Through this dynamic system, we can obtain a control design for target tracking on the sphere and the adapted topographic data provides an efficient agent trajectory. The topographic information, described as a form of friction in the double-integrator system, affects the velocity and acceleration of the target and agents. The target information required by the tracking agents consists of position, velocity, and acceleration. We can obtain practical rendezvous results when agents utilize only target position and velocity information. If the acceleration data of the target is accessible, we can get the complete rendezvous result using an additional control term in the form of the Coriolis force. We provide mathematically rigorous proofs for these results and present numerical experiments that can be visually confirmed.

Redox-Mediated pH Swing Systems for Electrochemical Carbon Capture.

ConspectusThe rising levels of atmospheric CO2 and their resulting impacts on the climate have necessitated the urgent development of effective carbon capture technologies. Electrochemical carbon capture systems have emerged as a potential alternative to conventional thermal systems based on amine solutions due to their modularity, energy efficiency, and lower environmental impact. Among these, aqueous electrochemical pH swing systems that capitalize on the pH dependence of dissolved inorganic carbon (CO2/HCO3-/CO32-) speciation to capture and release CO2 are of particular interest as they can be flexible in system design and in the range of electrochemical potentials used as well as being environmentally benign. In this Account, we present our recent findings in pH swing-based electrochemical carbon capture using redox-active materials, paving the way toward a sustainable solution for mitigating CO2 emissions.In the first section, we discuss the utilization of molecular redox-active organic materials in electrochemical carbon capture by the pH swing method. This electrochemical system configuration involves homogeneous aqueous electrolytes containing molecular redox-active compounds combined with inert carbon-based electrodes. We first present the development of redox-active amine and oxygen-insensitive neutral red (NR)-based systems. Notably, the discovery of 1-aminopyridinium (1-AP) as an electrochemically reversible compound enables efficient pH swing, leading to an impressive electron utilization of 1.25 mol of CO2 per mole of electrons. Additionally, we explore an oxygen-insensitive neutral red/leuconeutral red (NR/NRH2) redox system, which demonstrates potential applicability to direct air capture (DAC) systems with ambient air as a feed gas.The second section focuses on the utilization of inorganic nanomaterials for redox-active electrodes for pH swing-based electrochemical carbon capture. In this system configuration, we employ redox-active electrodes for inducing reversible pH swings in aqueous electrolytes without interrupting other ionic species, except protons. Specifically, we explore the effectiveness of manganese oxide (MnO2) electrodes for achieving selective CO2 removal from simulated flue gas. We then demonstrate a bismuth/silver (Bi/BiOCl, Ag/AgCl) nanoparticle electrode system as a sodium-insensitive pH swing system for extracting dissolved inorganic carbon (DIC) from simulated seawater with high electrochemical energy efficiency.Overall, these advances in pH swing-based electrochemical carbon capture offer promising preliminary solutions for combating climate change by capturing CO2 from dilute sources such as flue gas and ambient air as well as enabling direct carbon removal from ocean water. While these systems have demonstrated impressive energy efficiency and environmental benefits using redox-active materials, they represent only the beginning of our research journey. Further development and optimization are currently underway as we strive to unlock their full potential for large-scale implementation, paving the way toward a sustainable and carbon-neutral future.

Electrochemical direct air capture of CO2 using neutral red as reversible redox-active material.

Direct air capture of carbon dioxide is a viable option for the mitigation of CO2 emissions and their impact on global climate change. Conventional processes for carbon capture from ambient air require 230 to 800 kJ thermal per mole of CO2, which accounts for most of the total cost of capture. Here, we demonstrate electrochemical direct air capture using neutral red as a redox-active material in an aqueous solution enabled by the inclusion of nicotinamide as a hydrotropic solubilizing agent. The electrochemical system demonstrates a high electron utilization of 0.71 in a continuous flow cell with an estimated minimum work of 35 kJe per mole of CO2 from 15% CO2. Further exploration using ambient air (410 ppm CO2 in the presence of 20% oxygen) as a feed gas shows electron utilization of 0.38 in a continuous flow cell to provide an estimated minimum work of 65 kJe per mole of CO2.

On the modelling of spatially heterogeneous nonlocal diffusion: deciding factors and preferential position of individuals.

We develop general heterogeneous nonlocal diffusion models and investigate their connection to local diffusion models by taking a singular limit of focusing kernels. We reveal the link between the two groups of diffusion equations which include both spatial heterogeneity and anisotropy. In particular, we introduce the notion of deciding factors which single out a nonlocal diffusion model and typically consist of the total jump rate and the average jump length. In this framework, we also discuss the dependence of the profile of the steady state solutions on these deciding factors, thus shedding light on the preferential position of individuals.

Electrochemical Carbon Dioxide Capture and Release with a Redox-Active Amine.

Anthropogenic carbon dioxide (CO2) emission from the combustion of fossil fuels is a major contributor to global climate change and ocean acidification. The implementation of carbon capture and storage technologies has been proposed to mitigate the buildup of this greenhouse gas in the atmosphere. Among these technologies, direct air capture is regarded as a plausible CO2 removal tool whereby net negative emissions can be achieved. However, the separation of CO2 from air is particularly challenging due to the ultradilute concentration of CO2 in the presence of high concentrations of dioxygen and water. Here, we report a robust electrochemical redox-active amine system demonstrating a high electron utilization (i.e., mole of CO2 per mole of electrons) of up to 1.25 with the capture of two CO2 molecules per amine in an aqueous solution with a work of 101 kJe per moles of CO2. The capture of CO2 directly from ambient air as the feed gas presented an electron utilization of 0.78.

An Effective Algorithm to Find a Cost Minimizing Gateway Deployment for Node-Replaceable Wireless Sensor Networks.

In this paper, we present an efficient way to find a gateway deployment for a given sensor network topology. We assume that the expired sensors and gateways can be replaced and the locations of the gateways are chosen among the given sensor nodes. The objective is to find a gateway deployment that minimizes the cost per unit time, which consists of the maintenance and installation costs. The proposed algorithm creates a cost reference and uses it to find the optimal deployment via a divide and conquer algorithm. Comparing all cases is the most reliable way to find the optimal gateway deployment, but this is practically impossible to calculate, since its computation time increases exponentially as the number of nodes increases. The method we propose increases linearly, and so is suitable for large scale networks. Additionally, compared to stochastic algorithms such as the genetic algorithm, this methodology has advantages in computational speed and accuracy for a large number of nodes. We also verify our methodology through several numerical experiments.

Catalytic Generation and Use of Ketyl Radical from Unactivated Aliphatic Carbonyl Compounds.

Generation of a ketyl radical from unactivated aliphatic carbonyl compounds is an important strategy in organic synthesis. Herein, catalytic generation and use of a ketyl radical for the reductive coupling of aliphatic carbonyl compounds and styrenes by organic photoredox catalysis is described. The method is applicable to both aliphatic ketones and aldehydes to afford the corresponding tertiary and secondary alcohols in continuous flow and batch. Preliminary mechanistic investigation suggests the catalytic formation of a ketyl radical intermediate.

Peculiar Triarylamine-Based Co-assembled Supramolecular Polymers That Exhibit Two Transition Temperatures in the Formation of a Coiled Helical Bundle.

This paper describes the peculiar co-assembly supramolecular polymerization behavior of triphenylamine trisamide derivatives with d-alanine (T-ala) or glycine (T-gly) moieties. Concentration and temperature-dependent circular dichroism (CD) spectroscopy revealed that the heating curves of co-assemblies obtained at various molar ratios of T-ala to T-gly exhibited two distinct transition temperatures. The first transition was due to the transformation from coiled helical bundles to single helical fibers without handedness. The second was due to a change from typical elongation to nucleation. These phenomena were confirmed by solvent-dependent decoiling of coiled helical structures and concentration-dependent morphological analysis. The two transitioning temperatures were dependent on the concentration of T-ala in the co-assemblies, suggesting that T-ala concentration plays an important role in the formation of coiled helical bundles. Our study demonstrated the first observation of two distinct transition temperatures in supramolecular polymers.

Ni-Catalyzed Electrochemical Decarboxylative C-C Couplings in Batch and Continuous Flow.

An electrochemically driven, nickel-catalyzed reductive coupling of N-hydroxyphthalimide esters with aryl halides is reported. The reaction proceeds under mild conditions in a divided electrochemical cell and employs a tertiary amine as the reductant. This decarboxylative C(sp3)-C(sp2) bond-forming transformation exhibits excellent substrate generality and functional group compatibility. An operationally simple continuous-flow version of this transformation using a commercial electrochemical flow reactor represents a robust and scalable synthesis of value added coupling process.

Transfer and Dynamic Inversion of Coassembled Supramolecular Chirality through 2D-Sheet to Rolled-Up Tubular Structure.

Transfer and inversion of supramolecular chirality from chiral calix[4]arene analogs (3D and 3L) with an alanine moiety to an achiral bipyridine derivative (1) with glycine moieties in a coassembled hydrogel are demonstrated. Molecular chirality of 3D and 3L could transfer supramolecular chirality to an achiral bipyridine derivative 1. Moreover, addition of 0.6 equiv of 3D or 3L to 1 induced supramolecular chirality inversion of 1. More interestingly, the 2D-sheet structure of the coassembled hydrogels formed with 0.2 equiv of 3D or 3L changed to a rolled-up tubular structure in the presence of 0.6 equiv of 3D or 3L. The chirality inversion and morphology change are mainly mediated by intermolecular hydrogen-bonding interactions between the achiral and chiral molecules, which might be induced by reorientations of the assembled molecules, confirmed by density functional theory calculations.

Direct ß-Selective Hydrocarboxylation of Styrenes with CO2 Enabled by Continuous Flow Photoredox Catalysis.

The direct ß-selective hydrocarboxylation of styrenes under atmospheric pressure of CO2 has been developed using photoredox catalysis in continuous flow. The scope of this methodology was demonstrated with a range of functionalized terminal styrenes, as well as α-substituted and ß-substituted styrenes.

Photoredox activation of carbon dioxide for amino acid synthesis in continuous flow.

Although carbon dioxide (CO2) is highly abundant, its low reactivity has limited its use in chemical synthesis. In particular, methods for carbon-carbon bond formation generally rely on two-electron mechanisms for CO2 activation and require highly activated reaction partners. Alternatively, radical pathways accessed via photoredox catalysis could provide new reactivity under milder conditions. Here we demonstrate the direct coupling of CO2 and amines via the single-electron reduction of CO2 for the photoredox-catalysed continuous flow synthesis of α-amino acids. By leveraging the advantages of utilizing gases and photochemistry in flow, a commercially available organic photoredox catalyst effects the selective α-carboxylation of amines that bear various functional groups and heterocycles. The preliminary mechanistic studies support CO2 activation and carbon-carbon bond formation via single-electron pathways, and we expect that this strategy will inspire new perspectives on using this feedstock chemical in organic synthesis.

Stereoselective synthesis of 7-epi-incarvilline.

The enantioselective synthesis of 7-epi-incarvilline for formal syntheses of (-)-incarvilline, (+)-incarvine C, and (-)-incarvillateine is described. The key features of our synthesis involve (1) stereoselective construction of the optically active bicyclic lactone utilizing Pd(0)-catalyzed allylic alkylation, (2) efficient transformation of the bridged bicyclic lactone to the key bicyclic lactam skeleton, and (3) stereoselective elaborations of two stereocenters via a substrate-controlled catalytic hydrogenation and a 1,4-addition.

Triterpenoids and a sterol from the stem-bark of Styrax japonica and their protein tyrosine phosphatase 1B inhibitory activities.

Five pentacyclic triterpenoids (1-5) and a sterol (6) were isolated from the stem-bark of Styrax japonica. The six compounds, 1-6, were determined to be 3beta-acetoxy-28-hydroxyolean-12-ene (1), 3beta-acetoxyolean-12-en-28-acid (2), 3beta-acetoxyolean-12-en-28-aldehyde (3), 3beta-acetoxy-17beta-hydroxy-28-norolean-12-ene (4), taraxerol (5) and stigmasterol (6), respectively, by spectroscopic means, including the 2D-NMR technique. Compound 4 is a newly discovered natural compound. The protein tyrosine phosphatase 1B (PTP1B) inhibitory activities of the isolated compounds (1-6) were determined in vitro. Among the isolated compounds, 3beta-acetoxyolean-12-en-28-acid (2) and 3beta-acetoxyolean-12-en-28-aldehyde (3) had the most potent inhibitory PTP1B activity, with IC50 values of 7.8 and 9.3 microm, respectively.

A phenylpropanoid glycoside with antioxidant activity from Picria tel-ferae.

A phytochemical study on Picria tel-ferae resulted in the isolation of a phenylpropanoid glycoside (1), which was reported for the first time from this plant. The structure of compound 1 was identified as 1-O-3,4-(dihydroxyphenyl)- ethyl-beta-D- apiofuranosyl- (1-->4)-alpha-L-rharmnopyranosyl- (1-->3)-4-O-caffeoyl- beta-D-glucopyranoside on the basis of spectroscopic analyses. In addition, it was found that 1 exhibited a remarkable inhibitory effect on lipid peroxidation initiated by either a free radical [AAPH; 2,2'-azobis-(2-amidinopropane)dihydrochloride] or generated hydroxyl radical (Fe2+/ascorbate). These findings, together with those of previous studies, suggest that P. tel-ferae possesses abundant phenylpropanoid glycosides, and the plant might be used beneficially in the treatment of oxidative stress-related human diseases.