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Controlling the geometric structures of metal clusters through structural isomerization allows for tuning of their electronic state. In this study, we successfully synthesized butterfly-motif [PdAu8(PPh3)8]2+ (PdAu8-B, B means butterfly-motif) and [PtAu8(PPh3)8]2+ (PtAu8-B) by the structural isomerization from crown-motif [PdAu8(PPh3)8]2+ (PdAu8-C, C means crown-motif) and [PtAu8(PPh3)8]2+ (PtAu8-C), induced by association with anionic polyoxometalate, [Mo6O19]2– (Mo6) respectively, whereas their structural isomerization was suppressed by the use of [NO3]– and [PMo12O40]3– as counter anions. DR-UV-vis-NIR and XAFS analyses and density functional theory calculations revealed that the synthesized [PdAu8(PPh3)8][Mo6O19] (PdAu8-Mo6) and [PtAu8(PPh3)8][Mo6O19] (PtAu8-Mo6) had PdAu8-B and PtAu8-B respectively because PdAu8-Mo6 and PtAu8-Mo6 had bands in optical absorption at the longer wavelength region and different structural parameters characteristic of the butterfly-motif structure obtained by XAFS analysis. Single-crystal and powder X-ray diffraction analyses revealed that PdAu8-B and PtAu8-B were surrounded by six Mo6 with rock salt-type packing, which stabilizes the semi-stable butterfly-motif structure to overcome high activation energy for structural isomerization. Controlling the geometric structures of metal clusters through structural isomerization allows for tuning of their optical and catalytic properties. Here, structural isomerization of crown-motif clusters [PdAu8(PPh3)8]2+ and [PtAu8(PPh3)8]2+ to corresponding butterfly-motif clusters is induced using [Mo6O19]2- anions. [ABSTRACT FROM AUTHOR]

By facilitating a water/water phase separation (w/wPS), crowded biopolymers in cells form droplets that contribute to the spatial localization of biological components and their biochemical reactions. However, their influence on mechanical processes driven by protein motors has not been well studied. Here, we show that the w/wPS droplet spontaneously entraps kinesins as well as microtubules (MTs) and generates a micrometre-scale vortex flow inside the droplet. Active droplets with a size of 10–100 µm are generated through w/wPS of dextran and polyethylene glycol mixed with MTs, molecular-engineered chimeric four-headed kinesins and ATP after mechanical mixing. MTs and kinesin rapidly created contractile network accumulated at the interface of the droplet and gradually generated vortical flow, which can drive translational motion of a droplet. Our work reveals that the interface of w/wPS contributes not only to chemical processes but also produces mechanical motion by assembling species of protein motors in a functioning manner. Water/water phase separation in cells facilitates the spatial localization of biological components, but its influence on mechanical processes driven by protein motors has been largely overlooked. Here, the interface of water/water phase separation is shown to produce mechanical motion by spontaneously entrapping kinesins and microtubules and generating a micrometre-scale vortex flow inside cell-sized droplets. [ABSTRACT FROM AUTHOR]

In this study, we investigated the electrochemical intercalation of Ca2+ into graphite as an anode material for calcium-ion batteries (CIBs). The electrochemical intercalation of Ca2+ into a graphite electrode is possible when γ-butyrolactone (GBL) is utilized as a solvent, resulting in a reversible charge/discharge capacity. The GBL-based electrolyte allows a reversible redox reaction, thereby resulting in the intercalation and deintercalation of Ca2+ within the graphite electrode. Conversely, Ca2+ cannot be intercalated between the graphite layers in the ethylene carbonate–diethyl carbonate (EC–DEC)–based electrolyte. Analyses of the solution structures of both cases indicated that the interaction between the GBL solvent and Ca2+ was weak whereas that between the EC–DEC solvent and Ca2+ was strong. As a result of analyzing the surface of the negative electrode after charging and discharging from XPS, it was confirmed that a component that seems to be a solid electrolyte interphase (SEI) was confirmed in the graphite electrode using the GBL-based electrolyte. [ABSTRACT FROM AUTHOR]

Marine biomass such as seaweed and fishery waste is a potential energy source although it has not yet been practically utilized. This work focuses on renewable energy technologies, particularly anaerobic digestion, for the utilization of various organic wastes as energy resources. Primarily fundamental data for the efficient operation of an anaerobic digestion plant with marine biomass was obtained and a practical operation method was proposed using a simple model based on the carbon mass balance. Batch-processing experiments for seaweed, fishery waste and vegetable waste were carried out and each digestion characteristic was presented. The results indicate that fishery waste is the most efficient even though the accumulation of ammonium ions may inhibit methane production. Seaweeds are not efficient in either the production rate or the yield of methane gas. We investigated the efficient continuous operation for 6 biomass input scenarios with the proposed model. The results show that seaweed can be a useful supplement for the efficient operation. [ABSTRACT FROM AUTHOR]

Site-occupation embedding theory (SOET) is an in-principle-exact multi-determinantal extension of density-functional theory for model Hamiltonians. Various extensions of recent developments in SOET (Senjean et al. in Phys Rev B 97:235105, 2018) are explored in this work. An important step forward is the generalization of the theory to multiple-impurity sites. We also propose a new single-impurity density-functional approximation (DFA) where the density-functional impurity correlation energy of the two-level (2L) Hubbard system is combined with the Bethe ansatz local density approximation (BALDA) to the full correlation energy of the (infinite) Hubbard model. In order to test the new DFAs, the impurity-interacting wavefunction has been computed self-consistently with the density-matrix renormalization group method (DMRG). Double occupation and per-site energy expressions have been derived and implemented in the one-dimensional case. A detailed analysis of the results is presented, with a particular focus on the errors induced either by the energy functionals solely or by the self-consistently converged densities. Among all the DFAs (including those previously proposed), the combined 2L-BALDA is the one that performs the best in all correlation and density regimes. Finally, extensions in new directions, like a partition-DFT-type reformulation of SOET, a projection-based SOET approach, or the combination of SOET with Green functions, are briefly discussed as a perspective. [ABSTRACT FROM AUTHOR]

Controlling the geometric structures of metal clusters through structural isomerization allows for tuning of their electronic state. In this study, we successfully synthesized butterfly-motif [PdAu 8 (PPh 3 ) 8 ] 2+ (PdAu8-B, B means butterfly-motif) and [PtAu 8 (PPh 3 ) 8 ] 2+ (PtAu8-B) by the structural isomerization from crown-motif [PdAu 8 (PPh 3 ) 8 ] 2+ (PdAu8-C, C means crown-motif) and [PtAu 8 (PPh 3 ) 8 ] 2+ (PtAu8-C), induced by association with anionic polyoxometalate, [Mo 6 O 19 ] 2- (Mo6) respectively, whereas their structural isomerization was suppressed by the use of [NO 3 ] - and [PMo 12 O 40 ] 3- as counter anions. DR-UV-vis-NIR and XAFS analyses and density functional theory calculations revealed that the synthesized [PdAu 8 (PPh 3 ) 8 ][Mo 6 O 19 ] (PdAu8-Mo6) and [PtAu 8 (PPh 3 ) 8 ][Mo 6 O 19 ] (PtAu8-Mo6) had PdAu8-B and PtAu8-B respectively because PdAu8-Mo6 and PtAu8-Mo6 had bands in optical absorption at the longer wavelength region and different structural parameters characteristic of the butterfly-motif structure obtained by XAFS analysis. Single-crystal and powder X-ray diffraction analyses revealed that PdAu8-B and PtAu8-B were surrounded by six Mo6 with rock salt-type packing, which stabilizes the semi-stable butterfly-motif structure to overcome high activation energy for structural isomerization., (© 2023. The Author(s).)