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  1. Many of the unusual properties of Pluto’s orbit are widely accepted as evidence for the orbital migration of the giant planets in early solar system history. However, some properties remain an enigma. Pluto’s long-term orbital stability is supported by two special properties of its orbit that limit the location of its perihelion in azimuth and in latitude. We revisit Pluto’s orbital dynamics with a view to elucidating the individual and collective gravitational effects of the giant planets on constraining its perihelion location. While the resonant perturbations from Neptune account for the azimuthal constraint on Pluto’s perihelion location, we demonstrate that the long-term and steady persistence of the latitudinal constraint is possible only in a narrow range of additional secular forcing which arises fortuitously from the particular orbital architecture of the other giant planets. Our investigations also find that Jupiter has a largely stabilizing influence whereas Uranus has a largely destabilizing influence on Pluto’s orbit. Overall, Pluto’s orbit is rather surprisingly close to a zone of strong chaos. 
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  2. Abstract

    The prevalence of anion‐cation contacts in biomolecular recognition under aqueous conditions suggests that ionic interactions should dominate the binding of anions in solvents across both high and low polarities. Investigations of this idea using titrations in low polarity solvents are impaired by interferences from ion pairing that prevent a clear picture of binding. To address this limitation and test the impact of ion‐ion interactions across multiple solvents, we quantified chloride binding to a cationic receptor after accounting for ion pairing. In these studies, we created a chelate receptor using aryl‐triazole CH donors and a quinolinium unit that directs its cationic methyl inside the binding pocket. In low‐polarity dichloromethane, the 1 : 1 complex (logK1 : 1~ 7.3) is more stable than neutral chelates, but fortuitously comparable to a preorganized macrocycle (logK1 : 1~ 6.9). Polar acetonitrile and DMSO diminish stabilities of the charged receptor (logK1 : 1~ 3.7 and 1.9) but surprisingly 100‐fold more than the macrocycle. While both receptors lose stability by dielectric screening of electrostatic stability, the cationic receptor also pays additional costs of organization. Thus even though the charged receptor has stronger binding in apolar solvents, the uncharged receptor has more anion affinity in polar solvents.

     
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  3. Abstract

    In this paper, we highlight the uniqueness of nanoporous film‐coated electrodes as electrochemical sensing platforms. Specifically, we focus on discussing electrodes coated with insulator‐based monolithic films comprising vertically‐oriented, rigid cylindrical nanopores of uniform diameters (2–200 nm). The electrode coating results in the formation of an array of recessed nanodisk electrodes, and thus we named them recessed nanodisk‐array electrodes (RNEs). We first summarize the properties of nanoporous films commonly used for RNE fabrication, including nanoporous anodic alumina membranes, track‐etched polymer membranes, block copolymer‐derived nanoporous films, and mesoporous silica films. Subsequently, we discuss representative works that take advantage of the uniform size/shape of the nanopores for enhancing electrochemical detection selectivity and sensitivity. RNE‐based sensors measure faradaic currents from redox‐active analytes or exogenously‐added electroactive species that penetrate through the nanopores, or those from redox‐active moieties tethered to the surface of the nanopores or underlying electrodes. The enhanced detection selectivity of these sensors is attributed to the preferential partitioning of analytes into the nanopores or steric/electrostatic exclusion of interfering species. In particular, the uniform sizes/shapes of RNE nanopores play key roles in their higher molecular sieving selectivity and also in the better control of the detection selectivity based on electrostatic/chemical interactions. The detection sensitivity of RNE‐based sensors can be improved by tailoring the chemical environments of the nanopores for analyte preconcentration or for steric/electrostatic manipulation of the dynamics of redox‐tagged binding moieties. These unique characteristics of RNEs, in addition to the mitigation of electrode fouling by the nanoporous films, will enable the development of pretreatment‐free electrochemical sensors for complex matrix solutions.

     
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  4. Abstract

    Itokawa particles, which are samples recovered from the S-complex asteroid 25143 Itokawa by the Hayabusa spacecraft, demonstrate that S-complex asteroids are parent bodies of ordinary chondrite meteorites. Furthermore, they clarify that the space-weathering age of the Itokawa surface is of the order of several thousand years. Traditionally, Q-type asteroids have been considered fresh-surfaced. However, as the space-weathering timescale is approximately three orders of magnitude lesser than the conventionally considered age, the previously proposed formation mechanisms of Q-type asteroids cannot sufficiently explain the surface refreshening. In this study, we propose a new hypothesis on the surface state of Q-type asteroids: Q-type asteroids have a non-fresh weathered surface with a paucity of fine particles. For verifying this hypothesis, laboratory experiments on the space weathering of ordinary chondrites are performed. Based on the results of these experiments, we found that large (more than $100\, \mu \mathrm{m}$) ordinary chondritic particles with space weathering exhibit spectra consistent with Q-type asteroids.

     
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