Reversible Sodium Metal Electrodes: Is Fluorine an Essential Interphasial Component?

Alkaline metals are an ideal negative electrode for rechargeable batteries. Forming a fluorine‐rich interphase by a fluorinated electrolyte is recognized as key to utilizing lithium metal electrodes, and the same strategy is being applied to sodium metal electrodes. However, their reversible plating/stripping reactions have yet to be achieved. Herein, we report a contrary concept of fluorine‐free electrolytes for sodium metal batteries. A sodium tetraphenylborate/monoglyme electrolyte enables reversible sodium plating/stripping at an average Coulombic efficiency of 99.85 % over 300 cycles. Importantly, the interphase is composed mainly of carbon, oxygen, and sodium elements with a negligible presence of fluorine, but it has both high stability and extremely low resistance. This work suggests a new direction for stabilizing sodium metal electrodes via fluorine‐free interphases.     

Classical two-slit interference effects in double photoionization of molecular hydrogen at high energies

Recent experiments on double photoionization of H2 with photon energies between 160 and 240 eV have revealed body-frame angular distributions that suggest classical two-slit interference effects may be present when one electron carries most of the available energy and the second electron is not observed. We report precise quantum mechanical calculations that reproduce the experimental findings. They reveal that the interpretation in terms of classical diffraction is only appropriate at substantially higher photon energies. At the energies considered in the experiment we offer an alternative explanation based on the mixing of two nondiffractive contributions by circularly polarized light.     

Stable first-order particle-frame relativistic hydrodynamics for dissipative systems

We propose a stable first-order relativistic dissipative hydrodynamic equation in the particle frame (Eckart frame) for the first time. The equation to be proposed was in fact previously derived by the authors and a collaborator from the relativistic Boltzmann equation. We demonstrate that the equilibrium state is stable with respect to the time evolution described by our hydrodynamic equation in the particle frame. Our equation may be a proper starting point for constructing second-order causal relativistic hydrodynamics, to replace Eckart's particle-flow theory.     

Tuning the Electronic Properties and Acid‐Response Behavior of N‐Heteroacene‐Based π‐Conjugated Liquids by Changing the Number of π‐Conjugated Substituents

We have designed and synthesized two room‐temperature‐fluorescent π‐conjugated liquids based on the N‐heteroacene framework ( 1 and 2 ). These two π‐conjugated liquids, which contained one and two thiophene rings, respectively, exhibited different electronic properties and rheology behaviors. Single‐crystal X‐ray analysis of dithiophene‐appended compound 4 revealed that two thiophene rings hindered the interactions of the imino N atoms with acids through the formation of interactions between the S atoms of the thiophene rings and the imino N atoms of the pyrazine group. On the other hand, monothiophene‐appended molecules 1 and 3 each contained an unhindered imino N atom on the opposite site to the thiophene ring. Upon dissolving various acids with different pK_a values in compounds 1 and 2 , these slight structural differences gave rise to marked differences in their acid‐response behaviors, thereby resulting in the emission of variously colored fluorescence in the liquid state. Furthermore, when acids with lower pK_a values was dissolved in compounds 1 and 2 , phase transition occurred from an isotropic liquid state to a self‐organized liquid‐crystalline phase.     

Diastereoselective synthesis of useful building blocks by crotylation of beta-branched alpha-methylaldehydes with potassium crotyltrifluoroborates

The diastereoselective construction of stereotriads having consecutive methyl, hydroxy, and methyl substituents was realized by the substrate-controlled crotylation of beta-branched alpha-methylaldehydes with potassium crotyltrifluoroborates. Especially, crotylation of 2-(1,3-dithian-2-yl)propanal with potassium ( E)-crotyltrifluoroborate afforded, in good yield and with excellent diastereoselectivity, a useful building block that has different and potential functional groups on both ends.     

Donor-acceptor distance-dependence of photoinduced electron-transfer rate in flavoproteins

Ultrafast fluorescence quenching of flavin in flavodoxin from Megasphaera elsdenii was investigated by means of a fluorescence up-conversion method. Fluorescence lifetimes of flavodoxin from M. elsdenii were estimated to be tau(1) approximately 165 fs (0.97%) and tau(2) approximately 10 ps (0.03%). Correlation of photoinduced electron-transfer rates (k(ET)) with averaged distances (D(av)) between isoalloxazine and nearby tryptophan or tyrosine was examined and obtained an empirical equation of ln k(ET) vs D(av) by means of a nonlinear least-squares method using reported data together with flavodoxin from M. elsdenii. The values of D(av) were calculated from X-ray structures of the flavoproteins. The ln k(ET) was approximately linear at D(av) shorter than 7 A. The model free empirical equation was expressed as ln k(ET) = 29.7 + (-0.327 D(av) + 2.84 x 10(-5))/(0.698 - D(av)(2)). We also analyzed the observed values of ln k(ET) with Marcus theory, but could not obtain reasonable results. Our analysis suggests that the average distance, rather than the shortest (edge to edge) distance or interplanar angles between the aromatics rings, is the key factor in the process of the photoinduced electron transfer in these flavoproteins.     

One-pot amidation of olefins through Pd-catalyzed coupling of alkylboranes and carbamoyl chlorides

A one-pot synthesis of C1-elongated amides starting from olefins and carbamoyl chlorides has been developed. Alkylboranes, generated by hydroboration of terminal olefins with 9-BBN-H, underwent smooth coupling with carbamoyl chlorides in the presence of palladium catalyst and Cs2CO3.     

Synthesis of chiral oxime ethers based on regio- and enantioselective allylic substitution catalyzed by iridium-pybox complex

The oxygen atom of oximes acts as a reactive nucleophile in the iridium-catalyzed allylic substitution of unsymmetrical substrates to give the branched oxime ethers. Among several chiral ligands evaluated, the iridium complex of pybox ligand having phenyl group catalyzed the allylic substitution of phosphates with high activity to form the branched oxime ethers with good enantioselectivities.