Microscopic Elucidation of Solid‐Electrolyte Interphase (SEI) Film Formation via Atomistic Reaction Simulations: Importance of Functional Groups of Electrolyte and Intact Additive Molecules

Secondary batteries such as Li‐ion battery are expected to be utilized as not only ubiquitous electric power sources such as mobile phones but also large‐scale electricity storage devices. Therefore, it is urgent to develop the higher performance secondary batteries. Their lifetime and stability are found to be strongly dependent on the nature of passivation film called solid electrolyte interphase (SEI) film formed on the anode surface in the initial charge‐discharge cycle. However, since it is difficult to directly observe the film formation processes in experiment, its microscopic mechanism is still not found. On the other hand, although the theoretical methods are useful complement to the experiment, some new methodologies are necessary to understand the long‐term processes of SEI film, which is produced as a result of that a lot of chemical reactions proceed simultaneously. Under the circumstances, we have developed Red Moon method that can simulate such complex chemical reaction systems, and were able to analyze for the first time the SEI film formation processes on the anode surface at the atomistic level. Then, we clarified theoretically the microscopic mechanism of the additive effect which is essential to improve the Na‐ion battery performance so as to enhance the SEI film formation. This new microscopic insight must provide an important guiding principle for use in designing the most suitable electrolytes for developing high‐performance secondary batteries.     

Unusual regioselective intramolecular Diels-Alder reaction forming tricyclo[4.3.1.0(3,7)]decane system

The intramoleculae Diels-Alder reaction of cyclohexenone having an unsaturated ester side chain afforded tricyclo[4.3.1.0(3,7)]decanone in both a regio- and stereoselective manner under TMSCl-NEt(3)-ZnBr(2) conditions. Unexpectedly, the regiochemical control was against the conventional orbital requirement.     

An HPLC assay of hydroxyl radicals by the hydroxylation reaction of terephthalic acid

An HPLC assay for hydroxyl radicals is described. The hydroxyl radical was trapped by terephthalic acid (non-fluorescent), and 2-hydroxyl terephthalic acid (fluorescent) was quantitated by HPLC-fluorescence detection. At a terephthalic acid concentration of 4.25 mmol/L, the hydroxyl radical formed in the Fenton reaction was successfully assayed in the concentration range of hydrogen peroxide of 2.5-50 micro mol/L, where the concentration of Fe(II) was 50 micro mol/L. The fluorescence of 2-hydroxy terephthalate was stable at 24 h, and its detection limit by this method was 5 nmol/L (100 fmol).     

Selective formation of AAB- and ABC-type heterotrimeric alpha-helical coiled coils

The alpha-helical coiled coils have a representative amino acid sequence of (abcdefg)(n) heptad repeats. We previously reported that two peptides named IZ-2A and IZ-2W formed an (IZ-2A)(2)/IZ-2W heterotrimer with an Ala-Ala-Trp interaction in the hydrophobic core. In this paper, we describe the selective formation of AAB- and ABC-type heterotrimers. To increase the selectivity of the AAB-type heterotrimeric formation, Lys residues at the f position were mutated to either an Ala or a Gln residue to form IZ-2A(fA) or IZ-2W(fQ). Separately, both IZ-2A(fA) and IZ-2W(fQ) have a random structure at pH 7 and 20 degrees C. However, together IZ-2A(fA) and IZ-2W(fQ) form a 2:1 complex with a thermal transition midpoint (Tm) of 48 degrees C. This procedure was applied to prepare the ABC-type heterotrimer, in which two sets of Ala-Ala-Trp interactions were designed in the hydrophobic core. Interhelical interaction between the e and g positions and the alpha-helical propensity of the amino acid at the f position were also considered in the design. The resultant three peptides selectively formed the ABC-type heterotrimer with a Tm of 51 degrees C. Other peptide combinations had random coil properties.     

Synthesis and complexation of a novel cyclophane

A novel cyclophane, 17, 17, 40, 40-tetramethyl-7, 30-dinitro-1, 10, 24, 33-tetraoxa[2.2.1.2.2.1] metaparaparametaparaparacyclophane, was synthesized by 2:2 cyclization of 3,5-bis(bromomethyl)nitrobenzene, derived from 3,5-dimethylnitrobenzene, and bisphenol A. The cyclophane was found to form 1:1 complex with benzene.     

Highly Selective Copper‐Catalyzed Hydroboration of Allenes and 1,3‐Dienes

The highly selective copper‐catalyzed hydroboration of allenes has been developed. Allylboranes and alkenylboranes were selectively prepared by the judicious choice of catalytic species (copper hydride and boryl copper). Furthermore, two types of alkenylboranes could be selectively synthesized by the choice of an appropriate ligand. Mechanistic studies confirmed that the protonation of a (Z)‐σ‐allyl copper species, which was isolated and structurally characterized by single‐crystal X‐ray diffraction, was a key step in these reactions. Besides allenes, this method is also applicable to the selective hydroboration of 1,3‐diene derivatives to afford allylboranes and homoallylboranes.